Metathesis catalyst and process for use thereof

ABSTRACT

This invention relates to a catalyst compound for the metathesis of olefins represented by the formula: 
     
       
         
         
             
             
         
       
         
         
           
             wherein M is a Group 8 metal; X and X 1  are anionic ligands; L is a neutral two electron donor; L 1  is N, O, P, or S, preferably N or O; R is a C 1  to C 30  hydrocarbyl or a C 1  to C 30  substituted hydrocarbyl; G* is selected from the group consisting of hydrogen, a C 1  to C 30  hydrocarbyl, and a C 1  to C 30  substituted hydrocarbyl; R 1  is selected from the group consisting of hydrogen, a C 1  to C 30  hydrocarbyl, and a C 1  to C 30  substituted hydrocarbyl; and G is independently selected from the group consisting of hydrogen, halogen, C 1  to C 30  hydrocarbyls and C 1  to C 30  substituted hydrocarbyls. 
           
         
       
    
     This invention also relates to process to make alphaolefins comprising contacting an olefin, such as ethylene, with a feed oil containing a triacylglyceride (typically a fatty acid ester (such as methyl oleate)) with the catalyst compound described above. The fatty acid ester may be a fatty acid methyl ester derived from biodiesel.

STATEMENT OF RELATED APPLICATIONS

This invention is related to U.S. Ser. No. 61/259,521, filed Nov. 9,2009 and U.S. Ser. No. 61/259,514, filed Nov. 9, 2009.

FIELD OF THE INVENTION

This invention relates to olefin metathesis, more particularly,metathesis catalyst compounds and processes for the use thereof.

BACKGROUND OF THE INVENTION

The cross-metathesis of two reactant olefins, where each reactant olefincomprises at least one unsaturation site, to produce new olefins whichare different from the reactant olefins is of significant commercialimportance. The cross-metathesis reaction is usually catalyzed by one ormore catalytic metals, usually one or more transition metals.

One such commercially significant application is the cross-metathesis ofethylene and internal olefins to produce alpha-olefins, which isgenerally referred to as ethenolysis. In particular, thecross-metathesis of ethylene and an internal olefin to produce linearalpha-olefins (LAOS) is of particular commercial significance. LAOs areuseful as monomers or comonomers in certain (co)polymers(polyalphaolefins or PAOs) and/or as intermediates in the production ofepoxides, amines, oxo alcohols, synthetic lubricants, synthetic fattyacids and alkylated aromatics. Olefins Conversion Technology™, basedupon the Phillips Triolefin Process, is an example of an ethenolysisreaction converting ethylene and 2-butene into propylene. Theseprocesses use heterogeneous catalysts, such as tungsten and rheniumoxides, which have not proven effective for internal olefins containingfunctional groups such as cis-methyl oleate, a fatty acid methyl ester.

Methods for the production of polyalpha-olefins are typically multi-stepprocesses that often create unwanted by-products and waste of reactantsand energy. Full range linear alpha-olefins plants are petroleum-based,are inefficient and result in mixtures of oligomerization products thattypically yield Schulz-Flory distributions producing large quantities ofundesirable materials. In recent years there have been new technologiesimplemented to produce “on purpose” linear alpha-olefins such 1-hexeneand 1-octene through chromium-based selective ethylene trimerization ortetramerization catalysts. Alternatively, 1-octene has been produced viathe telomerization of butadiene and methanol. Similar strategies are notcurrently available for the production of 1-decene.

1-Decene is a co-product typically produced in the cross-metathesis ofethylene and methyl oleate. Alkyl oleates are fatty acid esters that canbe major components in biodiesel produced by the transesterification ofalcohol and vegetable oils. Vegetable oils containing at least one siteof unsaturation include canola, soybean, palm, peanut, mustard,sunflower, tung, tall, perilla, grapeseed, rapeseed, linseed, safflower,pumpkin corn and many other oils extracted from plant seeds. Alkylerucates similarly are fatty acid esters that can be major components inbiodiesel. Useful biodiesel compositions are those which typically havehigh concentrations of oleate and erucate esters. These fatty acidesters preferably have one site of unsaturation such thatcross-metathesis with ethylene yields 1-decene as a co-product.

Biodiesel is a fuel prepared from renewable sources, such as plant oilsor animal fats. To produce biodiesel, triacylglycerides (“TAG”), themajor compound in plant oils and animal fats, are converted to fattyacid alkyl esters (“FAAE,” i.e. biodiesel) and glycerol via reactionwith an alcohol in the presence of a base, acid, or enzyme catalyst.Biodiesel fuel can be used in diesel engines, either alone or in a blendwith petroleum-based diesel, or can be further modified to produce otherchemical products.

Cross-metathesis catalysts reported thus far for the ethenolysis ofmethyl oleate are typically ruthenium-based catalysts bearing phosphineor carbene ligands. Dow researchers in 2004 achieved catalysts turnoversof approximately 15,000 using the 1^(st) generation Grubb's catalyst,bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride,(Organometallics 2004, 23, 2027). Researchers at Materia, Inc. havereported turnover numbers up to 35,000 using a ruthenium catalystcontaining a cyclic alkyl amino carbene ligand, (WO 2008/010961). Theseturnovers were obtained with a catalyst reportedly too expensive forindustrial consideration due to high costs associated with the catalystsbeing derived from a low yielding synthesis (See Final Technical Reportentitled “Platform Chemicals from an Oilseed Biorefinery” grant numberDE-FG36-04GO14016 awarded by the Department of Energy). Additionally,the introduction of chelating isopropoxybenzylidene ligands has led toruthenium catalysts with improved activities for metathesis reactions(J. Am. Chem. Soc. 1999, 121, 791). However, these ruthenium alkylidenecatalysts are usually prepared by the reaction of ruthenium species withdiazo compounds. The concerns associated with industrial scale reactionscomprising diazo compounds have led to increased efforts to prepareruthenium alkylidenes via alternate synthetic routes, such as usingterminal alkynes or propargyl alcohols.

The synthesis of RuCl₂(PCy₃)₂(3-phenylindenylene) has proven useful inproviding an easy route to ruthenium alkylidenes which avoids costlydiazo preparations (Platinum Metals Rev. 2005, 49, 33). Also, Furstneret al. have prepared(N,N′-bis(mesityl)imidazol-2-ylidene)RuCl₂(3-phenylindenylene). Howeverthese types of complexes have not proven effective in ethenolysisreactions.

In order to obtain an economically viable process for 1-deceneproduction via the cross-metathesis of ethylene and biodiesel (such asanimal or vegetable oils), higher activity catalysts must be discovered.Thus there is a need for higher activity processes that produce desiredproducts and co-products in commercially desirable ratios.

There remains a need for catalysts which demonstrate high activity andselectivity in metathesis cross-reactions, including ethenolysis, whichare capable of being synthesized by both mild and affordable syntheticroutes. The instant invention's metathesis catalyst compounds provideboth a mild and commercially economical and an “atom-economical” routeto desirable olefins, in particular alpha-olefins, which in turn may beuseful in the preparation of PAOs. More particularly, instantinvention's metathesis catalyst compounds demonstrate improved activityand selectivity towards ethenolysis products in ethylenecross-metathesis reactions.

SUMMARY OF THE INVENTION

This invention relates to a metathesis catalyst compound represented bythe formula:

wherein M is a Group 8 metal; X and X¹ are anionic ligands; L is aneutral two electron donor; L¹ is N, O, P, or S, preferably N or O; G*is selected from the group consisting of hydrogen, a C₁ to C₃₀hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R is a C₁ to C₃₀hydrocarbyl or a C₁ to C₃₀ substituted hydrocarbyl; R¹ is selected fromthe group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl, and a C₁ toC₃₀ substituted hydrocarbyl; and G is independently selected from thegroup consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbyls and C₁ toC₃₀ substituted hydrocarbyls.

This invention also relates to a process to produce alpha olefin(preferably 1-decene) comprising contacting the metathesis catalystdescribed above with an olefin (preferably ethylene), and one or moretriacylglycerides such as fatty acid esters (preferably fatty acidmethyl esters, preferably methyl oleate).

In a preferred embodiment, this relates to a process to produce alphaolefin (preferably 1-decene) comprising contacting the metathesiscatalyst described above with an olefin (preferably ethylene), and oneor more triacylglycerides such as fatty acid esters (preferably fattyacid methyl esters, preferably methyl oleate) derived from biodiesel.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a representation of the molecular structure of(PPh₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene) (J)drawn with 30% thermal ellipsoids.

DETAILED DESCRIPTION

The present invention comprises a novel metathesis catalyst compounduseful for the cross-metathesis of olefins, and processes for the usethereof. More particularly, the present invention comprises a novelmetathesis catalyst compound which comprises a chelating indenylenegroup. Even more particularly, the present invention comprises a novelmetathesis catalyst compound which demonstrates improved activity andselectivity towards ethenolysis products in ethylene cross-metathesisreactions.

This invention also relates to a process comprising contacting a feedoil or derivative thereof (and optional alkene) with an olefinmetathesis catalyst under conditions which yield an alpha-olefin.Typically the feed oil is esterified or transesterified with an alcoholprior to contacting with the olefin metathesis catalyst.

This invention also relates to a process comprising contacting atriacylglyceride or a derivative thereof with an optional alkene (suchas ethylene) and an olefin metathesis catalyst under conditions whichyield an alpha-olefin, typically yielding a linear alpha-olefin (such as1-decene, 1-heptene, and/or 1-butene) and an ester or acidfunctionalized olefin.

This invention further relates to a process for producing alpha-olefins(preferably linear alpha-olefins) comprising contacting atriacylglyceride with an alcohol (such as methanol) to produce a fattyacid alkyl ester and thereafter contacting the fatty acid alkyl esterwith an olefin metathesis catalyst (and optional alkene, such asethylene) under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to a process for producing alpha-olefins(preferably linear alpha-olefins) comprising contacting atriacylglyceride with water and or an alkaline reactant (such as sodiumhydroxide) to produce a fatty acid and thereafter contacting the fattyacid with an olefin metathesis catalyst (and optional alkene, such asethylene) under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to contacting unsaturated fatty acid withan alkene (such as ethylene) in the presence of an olefin metathesiscatalyst under conditions which yield an alpha-olefin (preferably alinear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene)and an ester or acid functionalized olefin.

This invention further relates to contacting an unsaturated fatty acidester with an alkene (such as ethylene) in the presence of an olefinmetathesis catalyst under conditions which yield an alpha-olefin(preferably a linear alpha-olefin, preferably 1-decene, 1-heptene,and/or 1-butene) and an ester or acid functionalized olefin.

This invention further relates to contacting an unsaturated fatty acidalkyl ester with an alkene (such as ethylene) in the presence of anolefin metathesis catalyst under conditions which yield an alpha-olefin(preferably a linear alpha-olefin, preferably 1-decene, 1-heptene,and/or 1-butene) and an ester or acid functionalized olefin.

This invention also relates to a process to produce alpha olefin(preferably linear alpha olefin, preferably 1-decene, 1-heptene and or1-butene) comprising contacting a metathesis catalyst with an alkene(preferably ethylene), and one or more fatty acid esters (preferablyfatty acid methyl esters, preferably methyl oleate).

In a preferred embodiment, this relates to a process to produce alphaolefin (preferably linear alpha olefin, preferably 1-decene, 1-hepteneand or 1-butene) comprising contacting a metathesis catalyst with analkene (preferably ethylene), and one or more fatty acid esters(preferably fatty acid methyl esters, preferably methyl oleate) derivedfrom biodiesel.

In a preferred embodiment, the olefin metathesis catalysts describedherein may be combined directly with feed oils, triacylglycerides,biodiesel, fatty acids, fatty acid esters and/or fatty acid alkyl estersto produce alpha-olefins, preferably linear alpha olefins, preferably C₄to C₂₄ alpha-olefins, preferably linear alpha-olefins, such as 1-decene,1-heptene and or 1-butene.

In a preferred embodiment, a mixture of one or more biodiesels,triacylglycerides, fatty acids, fatty acid esters and/or fatty acidalkyl esters is used to produce alpha-olefins, preferably linear alphaolefins, preferably C₄ to C₂₄ alpha-olefins, preferably C₄ to C₂₄ linearalpha-olefins. In a preferred embodiment a mixture of alpha olefins,preferably linear alpha olefins, preferably 1-decene, 1-heptene and or1-butene is produced.

Process

In a preferred embodiment, the metathesis catalysts described herein maybe combined directly with feed oils, seed oils, biodiesel,triacylglycerides, fatty acids, fatty acid esters and/or fatty acidalkyl esters (“feed materials”) to produce alpha-olefins, preferablylinear alpha olefins, preferably C₄ to C₂₄ alpha-olefins, preferably C₄to C₂₄ linear alpha-olefins, such as preferably 1-decene, 1-heptene andor 1-butene.

Typically, the molar ratio of alkene to unsaturated feed material (suchas unsaturated fatty acid or fatty acid ester) is greater than about0.8/1.0, preferably greater than about 0.9/1.0. Typically, the molarratio of alkene to feed material (such as unsaturated fatty acid orfatty acid ester) is less than about 3.0/1.0, preferably less than about2.0/1.0. Depending upon the specific reagents, other molar ratios mayalso be suitable. With ethylene, for example, a significantly highermolar ratio can be used, because the self-metathesis of ethyleneproduces only ethylene again; no undesirable co-product olefins areformed. Accordingly, the molar ratio of ethylene to feed material (suchas unsaturated fatty acid or fatty acid ester) may range from greaterthan about 0.8/1 to typically less than about 20/1.

The quantity of metathesis catalyst that is employed in the process ofthis invention is any quantity that provides for an operable metathesisreaction. Preferably, the ratio of moles of feed material (preferablyfatty acid ester and or fatty acid alkyl ester) to moles of metathesiscatalyst is typically greater than about 10:1, preferably greater thanabout 100:1, preferably greater than about 1000:1, preferably greaterthan about 10,000:1, preferably greater than about 25,000:1, preferablygreater than about 50,000:1, preferably greater than about 100,000:1.Alternately, the molar ratio of feed material (preferably fatty acidester and or fatty acid alkyl ester) to metathesis catalyst is typicallyless than about 10,000,000:1, preferably less than about 1,000,000:1,and more preferably less than about 500,000:1.

The contacting time of the reagents and catalyst in a batch reactor canbe any duration, provided that the desired olefin metathesis productsare obtained. Generally, the contacting time in a reactor is greaterthan about 5 minutes, and preferably greater than about 10 minutes.Generally, the contacting time in a reactor is less than about 25 hours,preferably less than about 15 hours, and more preferably less than about10 hours.

In a preferred embodiment, the reactants (for example, metathesiscatalyst; feed materials; optional alkene, optional alcohol, optionalwater, etc.) are combined in a reaction vessel at a temperature of 20 to300° C. (preferably 20 to 200° C., preferably 30 to 100° C., preferably40 to 60° C.) and an alkene (such as ethylene) at a pressure of 0.1 to1000 psi (0.7 kPa to 6.9 MPa) (preferably 20 to 400 psi (0.14 MPa to 2.8MPa), preferably 50 to 250 psi (0.34 MPa to 1.7 MPa)), if the alkene ispresent, for a residence time of 0.5 seconds to 48 hours (preferably0.25 to 5 hours, preferably 30 minutes to 2 hours).

In certain embodiments, where the alkene is a gaseous olefin, the olefinpressure is greater than about 5 psig (34.5 kPa), preferably greaterthan about 10 psig (68.9 kPa), and more preferably greater than about 45psig (310 kPa). When a diluent is used with the gaseous alkene, theaforementioned pressure ranges may also be suitably employed as thetotal pressure of olefin and diluent. Likewise, when a liquid alkene isemployed and the process is conducted under an inert gaseous atmosphere,then the aforementioned pressure ranges may be suitably employed for theinert gas pressure.

In a preferred embodiment, from about 0.005 nmoles to about 500 nmoles,preferably from about 0.1 to about 250 nmoles, and most preferably fromabout 1 to about 50 nmoles of the metathesis catalyst are charged to thereactor per 3 mmoles of feed material (such as triacylglycerides,biodiesel, fatty acids, fatty acid esters and/or fatty acid alkyl estersor mixtures thereof, preferably fatty acid esters) charged.

In a preferred embodiment, the alkene and an unsaturated fatty acidester or unsaturated fatty acid are co-metathesized to form first andsecond product olefins, preferably a reduced chain first productalpha-olefin and a second product reduced chain terminal ester oracid-functionalized alpha-olefin. As a preferred example, the metathesisof methyloleate with ethylene will yield co-metathesis products of1-decene and methyl-9-decenoate. Both products are alpha-olefins; thedecenoate also terminates in an ester moiety at the opposite end of thechain from the carbon-carbon double bond. In addition to the desiredproducts, the methyloleate may self-metathesize to produce small amountsof 9-octadecene, a less desirable product, anddimethyl-9-octadecene-1,18-dioate, CH₃OC(O)(CH₂)₇CH═CH(CH₂)₇C(O)OCH₃, asecond less desirable product.

In the process of this invention, the conversion of feed material(preferably fatty acid ester and or fatty acid alkyl ester) can varywidely depending upon the specific reagent olefins, the specificcatalyst, and specific process conditions employed. For the purpose ofthis invention, “conversion” is defined as the mole percentage of feedmaterial that is converted or reacted to the cross-metathesisalpha-olefin products. Typically, the conversion of feed material(preferably fatty acid ester and or fatty acid alkyl ester) is greaterthan about 50 mole percent, preferably greater than about 60 molepercent, and more preferably greater than about 70 mole percent.

In the process of this invention, the yields of first product olefin andester or acid-functionalized second product olefin can also varydepending upon the specific reagent olefins, catalyst, and processconditions employed. For the purposes of this invention “yield” will bedefined as the mole percentage of cross-metathesis alpha-olefin productolefin formed relative to the initial moles of feed material (such asfatty acid ester and or fatty acid alkyl ester) in the feed. Typically,the yield of alpha-olefin will be greater than about 35 mole percent,preferably greater than about 50 mole percent. Typically, the yield ofester or acid-functionalized alpha-olefin will be greater than about 35mole percent, preferably greater than about 50 mole percent.

In a preferred embodiment, the process is typically a solution process,although it may be a bulk or high pressure process. Homogeneousprocesses are preferred. (A homogeneous process is defined to be aprocess where at least 90 wt % of the product is soluble in the reactionmedia.) A bulk homogeneous process is particularly preferred. (A bulkprocess is defined to be a process where reactant concentration in allfeeds to the reactor is 70 volume % or more.) Alternately no solvent ordiluent is present or added in the reaction medium, (except for thesmall amounts used as the carrier for the catalyst or other additives,or amounts typically found with the reactants; e.g. propane inpropylene).

Suitable diluents/solvents for the process include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopar™); perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. Suitable diluents/solvents also include aromatichydrocarbons, such as toluene or xylenes, and chlorinated solvents, suchas dichloromethane. In a preferred embodiment, the feed concentrationfor the process is 60 volume % solvent or less, preferably 40 volume %or less, preferably 20 volume % or less.

The process may be batch, semi-batch or continuous. As used herein, theterm continuous means a system that operates without interruption orcessation. For example, a continuous process to produce a metathesisproduct would be one where the reactants are continually introduced intoone or more reactors and cross-metathesis alpha-olefin product iscontinually withdrawn.

Useful reaction vessels include reactors (including continuous stirredtank reactors, batch reactors, reactive extruder, pipe or pump.

The processes may be conducted in either glass lined, stainless steel orsimilar type reaction equipment. Useful reaction vessels includereactors (including continuous stirred tank reactors, batch reactors,reactive extruder, pipe or pump, continuous flow fixed bed reactors,slurry reactors, fluidized bed reactors, and catalytic distillationreactors). The reaction zone may be fitted with one or more internaland/or external heat exchanger(s) in order to control undue temperaturefluctuations, or to prevent “runaway” reaction temperatures.

If the process is conducted in a continuous flow reactor, then theweight hourly space velocity, given in units of grams feed material(preferably fatty acid ester and or fatty acid alkyl ester) per gramcatalyst per hour (h⁻¹), will determine the relative quantities of feedmaterial to catalyst employed, as well as the residence time in thereactor of the unsaturated starting compound. In a flow reactor, theweight hourly space velocity of the unsaturated feed material(preferably fatty acid ester and or fatty acid alkyl ester) is typicallygreater than about 0.04 g feed material (preferably fatty acid ester andor fatty acid alkyl ester) per g catalyst per hour (h⁻¹), and preferablygreater than about 0.1 h⁻¹. In a flow reactor, the weight hourly spacevelocity of the feed material (preferably fatty acid ester and or fattyacid alkyl ester) is typically less than about 100 h⁻¹, and preferablyless than about 20 h⁻¹.

In certain embodiments, reactions utilizing the catalytic complexes ofthe present invention can be run in a biphasic mixture of solvents, inan emulsion or suspension, or in a lipid vesicle or bilayer.

The feed material is typically provided as a liquid phase, preferablyneat. In particular embodiments, the feed material is provided in aliquid phase, preferably neat; while the alkene is provided as a gasthat is dissolved in the liquid phase. In certain embodiments, feedmaterial is an unsaturated fatty acid ester or unsaturated fatty acidand is provided in a liquid phase, preferably neat; while the alkene isa gaseous alpha-olefin, such as for example, ethylene, which isdissolved in the liquid phase.

Generally, the feed material is an unsaturated fatty acid ester orunsaturated fatty acid and is provided as a liquid at the processtemperature, and it is generally preferred to be used neat, that is,without a diluent or solvent. The use of a solvent usually increasesrecycle requirements and increases costs. Optionally, however, ifdesired, a solvent can be employed with the alkene and/or feed material.A solvent may be desirable, for instance, where liquid feed material andalkene are not entirely miscible, and both then can be solubilized in asuitable solvent.

In a preferred embodiment, the productivity of the process is at least200 g of linear alpha-olefin (such as decene-1) per mmol of catalyst perhour, preferably at least 5000 g/mmol/hour, preferably at least 10,000g/mmol/hr, preferably at least 300,000 g/mmol/hr. For the purposes ofthis invention, “productivity” is defined to be the amount in grams oflinear alpha-olefin produced per mmol of catalyst introduced into thereactor, per hour.

For the purposes of this invention, selectivity is a measure ofconversion of alkene and feed material to the cross-metathesisalpha-olefin product, and is defined by the mole percentage of productolefin formed relative to the initial moles of alkene or feed material.In a preferred embodiment, the selectivity of the process is at least 20wt % linear alpha-olefin, based upon the weight to the material exitingthe reactor, preferably at least 25%, preferably at least 30%,preferably at least 35%.

For the purpose of this invention, catalyst turnover number (TON) is ameasure of how active the catalyst compound is and is defined as thenumber of moles of cross-metathesis alpha-olefin product formed per moleof catalyst compound. In a preferred embodiment, the (TON), of theprocess is at least 10,000, preferably at least 50,000, preferably atleast 100,000, preferably at least 1,000,000.

In a preferred embodiment, the alpha olefin yield (when convertingunsaturated fatty acids, unsaturated fatty acid esters, unsaturatedfatty acid alkyl esters or mixtures thereof), defined as the molepercentage of cross metathesis alpha olefin product formed per mole ofunsaturated fatty acids, unsaturated fatty acid esters, unsaturatedfatty acid alkyl esters or mixtures thereof introduced into the reactor,is 30% or more, preferably 40% or more, preferably 45% or more,preferably 50% or more, preferably 55% or more, preferably 60% or more.

In a preferred embodiment, the yield for reactions (when convertingtriacylglycerides as represented in the formula below), is defined asthe moles of alpha olefin formed divided by (the moles of unsaturatedR^(a)+moles of unsaturated R^(b)+moles of unsaturated R^(c)) introducedinto the reactor is 30% or more, preferably 40% or more, preferably 45%or more, preferably 50% or more, preferably 55% or more, preferably 60%or more,

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor unsaturated hydrocarbon chain (preferably R^(a), R^(b) and R^(c)each, independently, are a C₁₂ to C₂₈ alkyl or alkene, preferably C₁₆ toC₂₂ alkyl or alkene).Alkenes

Besides the feed materials, the metathesis process of this invention mayuse an alkene as a reactant. The term “alkene” shall mean an organiccompound containing at least one carbon-carbon double bond. Alkenesuseful herein typically have less than about 10 carbon atoms. The alkenemay have one carbon-carbon unsaturated bond, or alternatively, two ormore carbon-carbon unsaturated bonds. Since the metathesis reaction canoccur at any double bond, alkenes having more than one double bond willproduce more metathesis products. Accordingly, in some embodiments, itis preferred to employ an alkene having only one carbon-carbon doublebond. The double bond may be, without limitation, a terminal double bondor an internal double bond. The alkene may also be substituted at anyposition along the carbon chain with one or more substituents, providedthat the one or more substituents are essentially inert with respect tothe metathesis process. Suitable substituents include, withoutlimitation, alkyl, preferably C₁₋₆ alkyl; cycloalkyl, preferably C₃₋₆cycloalkyl; as well as hydroxy, ether, keto, aldehyde, and halogenfunctionalities. Non-limiting examples of suitable alkenes includeethylene, propylene, butene, butadiene, pentene, hexene, the variousisomers thereof, as well as higher homologues thereof. Preferably, thealkene is a C₂₋₈ alkene. More preferably the alkene is a C₂₋₆ alkene,even more preferably a C₂₋₄ alkene, and most preferably ethylene.

Useful alkenes include those represented by the formula: R*—HC═CH—R*,wherein each R* is independently, hydrogen or a C₁ to C₂₀ hydrocarbyl,preferably hydrogen or a C₁ to C₆ hydrocarbyl, preferably hydrogen,methyl, ethyl, propyl or butyl, more preferably R* is hydrogen. In apreferred embodiment, both R* are the same, preferably both R*arehydrogen. Ethylene, propylene, butene, pentene, hexene, octene andnonene (preferably ethylene) are alkenes useful herein.

For purposes of this invention and the claims thereto, the term lowerolefin means an alkene represented by the formula: R*—HC═CH—R*, whereineach R* is independently, hydrogen or a C₁ to C₆ hydrocarbyl, preferablyhydrogen or a C₁ to C₃ hydrocarbyl, preferably hydrogen, methyl, ethyl,propyl or butyl, more preferably R* is hydrogen. In a preferredembodiment, both R* are the same, preferably both R*are hydrogen.Ethylene, propylene, butene, pentene, hexene, and octene (preferablyethylene) are lower olefins useful herein.

Triacylglycerides

Triacylglycerides (TAGs), also called triglycerides, are a naturallyoccurring ester of three fatty acids and glycerol that is the chiefconstituent of natural fats and oils. The three fatty acids can be alldifferent, all the same, or only two the same, they can be saturated orunsaturated fatty acids, and the saturated fatty acids may have one ormultiple unsaturations. Chain lengths of the fatty acids in naturallyoccurring triacylglycerides can be of varying lengths but 16, 18 and 20carbons are the most common Natural fatty acids found in plants andanimals are typically composed only of even numbers of carbon atoms dueto the way they are bio-synthesized. Most natural fats contain a complexmixture of individual triglycerides and because of this, they melt overa broad range of temperatures.

Biodiesel is a mono-alkyl ester derived from the processing of vegetableor animal oils and alcohols. The processing is typically carried out byan esterification reaction mechanism, and typically is performed in anexcess of alcohol to maximize conversion. Esterification can refer todirect esterification, such as between a free fatty acid and an alcohol,as well as transesterification, such as between an ester and an alcohol.While vegetable oil and alcohols are commonly employed as reactants inesterification reactions, a fatty acid source such as free fatty acids,soaps, esters, glycerides (mono-, di- tri-), phospholipids,lysophospholipids, or amides and a monohydric alcohol source, such as analcohol or an ester, can be esterified. In addition, variouscombinations of these reagents can be employed in an esterificationreaction.

Vegetable and animal oils include triglycerides and neutral fats, suchas triacylglyderides, the main energy storage form of fat in animals andplants. These typically have the chemical structure:

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor non-saturated hydrocarbon chain (preferably R^(a), R^(b) and R^(c)each, independently, are a C₁₂ to C₂₈ alkyl or alkene, preferably C₁₆ toC₂₂ alkyl or alkene). Different vegetable oils have different fatty acidprofiles, with the same or different fatty acids occurring on a singleglycerol. For example, an oil can have linoleic, oleic, and stearicacids attached to the same glycerol, with each of R^(a), R^(b) and R^(c)representing one of these three fatty acids. In another example, therecan be two oleic acids and one stearic acid attached to the sameglycerol, each of R^(a), R^(b) and R^(c) representing one of these fattyacids. A particularly useful triglyceride consists of three fatty acids(e.g., saturated fatty acids of general structure of CH₃(CH₂)_(n)COOH,wherein n is typically an integer of from 4 to 28 or higher) attached toa glycerol (C₃H₅(OH)₃) backbone by ester linkages. In the esterificationprocess, vegetable oils and short chain alcohols are reacted to formmono-alkyl esters of the fatty acid and glycerol (also referred to asglycerin). When the alcohol used is methanol (CH₃OH), a methyl ester iscreated with the general form CH₃(CH₂)_(n)COOCH₃ for saturated fattyacids. Typically, but not always, the length of the carbon backbonechain is from 12 to 24 carbon atoms.

The esterification process can be catalyzed or non-catalyzed. Catalyzedprocesses are categorized into chemical and enzyme based processes.Chemical catalytic methods can employ acid and/or base catalystmechanisms. The catalysts can be homogeneous and/or heterogeneouscatalysts. Homogeneous catalysts are typically liquid phase mixtures,whereas heterogeneous catalysts are solid phase catalysts mixed with theliquid phase reactants, oils and alcohols.

The fatty acid rich material useful in the processes described hereincan be derived from plant, animal, microbial, or other sources (feedoil). Preferred feed oils include vegetable oils such as corn, soy,rapeseed, canola, sunflower, palm and other oils that are readilyavailable; however, any vegetable oil or animal fat can be employed. Rawor unrefined oil can be used in certain embodiments; however, filteredand refined oils are typically preferred. Use of degummed and filteredfeedstock minimizes the potential for emulsification and blockage in thereactors. Feedstock with high water content can be dried before basiccatalyst processing. Feedstock with high free fatty acid content can bepassed through an esterification process to reduce the free fatty acidcontent before the process of esterification to convert fatty acidglycerides to monoalkyl esters. The reduction of free fatty acids andthe conversion of fatty acid glycerides can also in the same processingstep. Feedstock containing other organic compounds (such as hexane,heptane, isohexane, etc.) can typically be processed without significantmodifications to the reactor. Other materials containing fatty acidglycerides or other fatty acid esters can also be employed, includingphospholipids, lysophospholipids, and fatty acid wax esters. The fattyacid rich material useful in the processes described herein typicallyincludes a mixture of fatty acids. For example, the fatty acid profilesof several useful feedstocks are shown in Table 1. The feed oil used asfeedstock can also include a mixture of fatty acid glycerides fromdifferent sources. The free fatty acid content of useful vegetable oilsis preferably about 0.1 wt % or less when employed in a basichomogeneous catalyst esterification reaction. Higher levels can beutilized as well, and levels up to about 3 wt %, or even as high as 15wt % or more can typically be tolerated.

TABLE 1 Fatty Acid Profile of Several Typical Feed Oils High Oleic Fatty(a.k.a. Hi Oleic) Yellow Acid Palm Oil Soy Oil Rapeseed Grease 0 wt % 0wt % 0 wt % 0 wt % C6:0 0 wt % 0 wt % 0 wt % 0 wt % C8:0 0 wt % 0 wt % 0wt % 0 wt % C10:0 0 wt % 0 wt % 0 wt % 0 wt % C12:0 0 wt % 0 wt % 0 wt %0 wt % C14:0 1 wt % 0 wt % 0 wt % 2 wt % C16:0 44 wt %  7 wt % 4 wt % 23wt %  C18:0 5 wt % 5 wt % 1 wt % 13 wt %  C18:1 39 wt %  28 wt %  60 wt%  44 wt %  C18:2 10 wt %  53 wt %  21 wt %  7 wt % C18:3 0 wt % 0 wt %13 wt %  1 wt % C20:0 0 wt % 0 wt % 0 wt % 0 wt % C22:1 0 wt % 0 wt % 0wt % 0 wt % Misc. 1 wt % 8 wt % 0 wt % 9 wt % Total 100 wt %  100 wt % 100 wt %  100 wt % Alcohol (Also Referred to as Alkanols)

The alcohol used herein can be any monohydric, dihydric, or polyhydricalcohol that is capable of condensing with the feed material (such asthe unsaturated fatty acid) to form the corresponding unsaturated ester(such as the fatty acid ester). Typically, the alcohol contains at leastone carbon atom. Typically, the alcohol contains less than about 20carbon atoms, preferably less than about 12 carbon atoms, and morepreferably less than about 8 carbon atoms. The carbon atoms may bearranged in a straight-chain or branched structure, and may besubstituted with a variety of substituents, such as those previouslydisclosed hereinabove in connection with the fatty acid, including theaforementioned alkyl, cycloalkyl, monocyclic aromatic, arylalkyl,alkylaryl, hydroxyl, halogen, ether, ester, aldehyde and ketosubstituents. Preferably, the alcohol is a straight-chain or branchedC₁₋₁₂ alkanol. A preferred alcohol is the trihydric alcohol glycerol,the fatty acid esters of which are known as “glycerides.” Otherpreferred alcohols include methanol and ethanol.

Preferably, the alcohol employed in the esterification and/ortransesterification reactions is preferably a low molecular weightmonohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol,1-butanol, 2-butanol, or t-butanol. The alcohol is preferably anhydrous;however, a small amount of water in the alcohol may be present (e.g.,less than about 2 wt %, preferably less than about 1 wt %, and mostpreferably less than about 0.5 wt %; however in certain embodimentshigher amounts can be tolerated). Acid esterification reactions are moretolerant of the presence of small amounts of water in the alcohol thanare basic transesterification reactions. While specific monohydricalcohols are discussed herein with reference to certain embodiments andexamples, the preferred embodiments are not limited to such specificmonohydric alcohols. Other suitable monohydric alcohols can also beemployed in the preferred embodiments.

Transesterification/Esterification Reactions

The conversion of TAGs to fatty acid alkyl esters (“FAAE”) throughtransesterification of the TAG typically involves forming a reactantstream, which includes TAG (e.g., at least about 75 wt %), alkanol(e.g., about 5 wt % to 20 wt %), a transesterification catalyst (e.g.,about 0.05 wt % to 1 wt %), and optionally, glycerol (typically up toabout 10 wt %). Suitable alkanols may include C1-C6 alkanols andcommonly may include methanol, ethanol, or mixtures thereof. Suitabletransesterification catalysts may include alkali metal alkoxides havingfrom 1 to 6 carbon atoms and commonly may include alkali metalmethoxide, such as sodium methoxide and/or potassium methoxide. Thebasic catalyst is desirably selected such that the alkali metal alkoxidemay suitably contain an alkoxide group which is the counterpart of thealkanol employed in the reaction stream (e.g., a combination of methanoland an alkali metal methoxide such as sodium methoxide and/or potassiummethoxide). The reactant stream may suitably include about 0.05 wt % to0.3 wt % sodium methoxide, at least about 75 wt % triacylglyceride,about 1 wt % to 7 wt % glycerol, and at least about 10 wt % methanol. Insome embodiments, the reactant stream may desirably include about 0.05wt % to 0.25 wt % sodium methoxide, at least about 75 wt %triacylglyceride, about 2 wt % to 5 wt % glycerol, and about 10 wt % to15 wt % methanol.

The rate and extent of reaction for esterification of the fatty acidglycerides or other fatty acid derivates with monohydric alcohol in thepresence of a catalyst depends upon factors including but not limited tothe concentration of the reagents, the concentration and type ofcatalyst, and the temperature and pressure conditions, and time ofreaction. The reaction generally proceeds at temperatures above about50° C., preferably at temperatures above 65° C.; however, the catalystselected or the amount of catalyst employed can affect this temperatureto some extent. Higher temperatures generally result in faster reactionrates. However, the use of very high temperatures, such as those inexcess of about 300° C., or even those in excess of 250° C., can lead toincreased generation of side products, which can be undesirable as theirpresence can increase downstream purification costs. Higher temperaturescan be advantageously employed, however, e.g., in situations where theside products do not present an issue.

The reaction temperature can be achieved by preheating one or more ofthe feed materials or by heating a mixture of the feed materials.Heating can be achieved using apparatus known in the art e.g., heatexchangers, jacketed vessels, submerged coils, and the like. Whilespecific temperatures and methods of obtaining the specific temperaturesare discussed herein with reference to certain embodiments and examples,the preferred embodiments are not limited to such specific temperaturesand methods of obtaining the specific temperatures. Other temperaturesand methods of obtaining temperatures can also be employed in thepreferred embodiments.

The amount of alcohol employed in the reaction is preferably in excessof the amount of fatty acid present on a molar basis. The fatty acid canbe free or combined, such as to alcohol, glycol or glycerol, with up tothree fatty acid moieties being attached to a glycerol. Additionalamounts of alcohol above stoichiometric provide the advantage ofassisting in driving the equilibrium of the reaction to produce more ofthe fatty acid ester product. However, greater excesses of alcohol canresult in greater processing costs and larger capital investment for thelarger volumes of reagents employed in the process, as well as greaterenergy costs associated with recovering, purifying, and recycling thisexcess alcohol. Accordingly, it is generally preferred to employ anamount of alcohol yielding a molar ratio of alcohol to fatty acid offrom about 15:1 to about 1:1 (stoichiometric), and more preferably fromabout 4:1 to about 2:1; however, the process can operate over a muchwider range of alcohol to fatty acid ratios, with nonreacted materialssubjected to recycling or other processing steps. Generally, lowerrelative levels of alcohol to fatty acid result in decreased yield andhigher relative levels of alcohol levels to fatty acid result inincreased capital and operating expense. Some instances of operation atratios of alcohol to fatty acid over a wider range include when firststarting up the process or shutting down the process, when balancing thethroughput of the reactor to other processing steps or other processingfacilities, such as one that produces alcohol or utilizes a side stream,or when process upsets occur. When a molar ratio of 2:1 methanol tofatty acid is employed and a sodium hydroxide concentration of about 0.5wt % of the total reaction mixture is employed, the ratio of sodiumhydroxide to methanol is about 2 wt % entering the reactor and about 4wt % at the exit because about half of the alcohol is consumed in theesterification reaction.

Similarly, higher amounts of catalyst generally result in fasterreactions. However, higher amounts of catalyst can lead to higherdownstream separation costs and a different profile of side reactionproducts. The amount of homogeneous catalyst is preferably from about0.2 wt % to about 1.0 wt % of the reaction mixture when the catalyst issodium hydroxide; at typical concentration of 0.5 wt % when a 2:1 molarratio of methanol to fatty acid is used; however, in certain embodimentshigher or lower amounts can be employed. The amount of catalyst employedcan also vary depending upon the nature of the catalyst, feed materials,operating conditions, and other factors. Specifically, the temperature,pressure, free fatty acid content of the feed, and degree of mixing canchange the amount of catalyst preferably employed. While specificcatalyst amounts are discussed herein with reference to certainembodiments and examples, the preferred embodiments are not limited tosuch specific catalyst amounts. Other suitable catalyst amounts can alsobe employed in the preferred embodiments.

The esterification reaction can be performed batchwise, such as in astirred tank, or it can be performed continuously, such as in acontinuous stirred tank reactor (CSTR) or a plug flow reactor (PFR).When operated in continuous mode, a series of continuous reactors(including CSTRs, PFRs, or combinations thereof) can advantageouslyoperate in series. Alternatively, batch reactors can be arranged inparallel and/or series.

When the reactor is operated in a continuous fashion, one or more of thefeed materials is preferably metered into the process. Varioustechniques for metering can be employed (e.g., metering pumps, positivedisplacement pumps, control valves, flow meters, and the like). Whilespecific types of reactors are discussed herein with reference tocertain embodiments and examples, the preferred embodiments are notlimited to such specific reactors. Other suitable types of reactors canalso be employed in the preferred embodiments.

Fatty Acids and Fatty Acid Esters

Fatty acids are carboxylic acids with a saturated or unsaturatedaliphatic tails that are found naturally in many different fats andoils. Any unsaturated fatty acid can be suitably employed in the processof this invention, provided that the unsaturated fatty acid can bemetathesized in the manner disclosed herein. An unsaturated fatty acidcomprises a long carbon chain containing at least one carbon-carbondouble bond and terminating in a carboxylic acid group. Typically, theunsaturated fatty acid will contain greater than about 8 carbon atoms,preferably greater than about 10 carbon atoms, and more preferablygreater than about 12 carbon atoms. Typically, the unsaturated fattyacid will contain less than about 50 carbon atoms, preferably less thanabout 35 carbon atoms, and more preferably less than about 25 carbonatoms. At least one carbon-carbon double bond is present along thecarbon chain, this double bond usually occurring about the middle of thechain, but not necessarily. The carbon-carbon double bond may also occurat any other internal location along the chain. A terminal carbon-carbondouble bond, at the opposite end of the carbon chain relative to theterminal carboxylic acid group, is also suitably employed, althoughterminal carbon-carbon double bonds occur less commonly in fatty acids.Unsaturated fatty acids containing the terminal carboxylic acidfunctionality and two or more carbon-carbon double bonds may also besuitably employed in the process of this invention. Since metathesis canoccur at any of the carbon-carbon double bonds, a fatty acid having morethan one double bond may produce a variety of metathesis products. Theunsaturated fatty acid may be straight or branched and substituted alongthe fatty acid chain with one or more substituents, provided that theone or more substituents are substantially inert with respect to themetathesis process. Non-limiting examples of suitable substituentsinclude alkyl moieties, preferably C₁₋₁₀ alkyl moieties, including, forexample, methyl, ethyl, propyl, butyl, and the like; cycloalkylmoieties, preferably C₄₋₈ cycloalkyl moieties, including for example,cyclopentyl and cyclohexyl; monocyclic aromatic moieties, preferably C₆aromatic moieties, that is, phenyl; arylalkyl moieties, preferably C₇₋₁₆arylalkyl moieties, including, for example, benzyl; and alkylarylmoieties, preferably C₇₋₁₆ alkylaryl moieties, including, for example,tolyl, ethylphenyl, xylyl, and the like; as well as hydroxyl, ether,keto, aldehyde, and halide, preferably chloro and bromo,functionalities.

Non-limiting examples of suitable unsaturated fatty acids include3-hexenoic (hydrosorbic), trans-2-heptenoic, 2-octenoic, 2-nonenoic,cis- and trans-4-decenoic, 9-decenoic (caproleic), 10-undecenoic(undecylenic), trans-3-dodecenoic (linderic), tridecenoic,cis-9-tetradeceonic (myristoleic), pentadecenoic, cis-9-hexadecenoic(cis-9-palmitoelic), trans-9-hexadecenoic (trans-9-palmitoleic),9-heptadecenoic, cis-6-octadecenoic (petroselinic), trans-6-octadecenoic(petroselaidic), cis-9-octadecenoic (oleic), trans-9-octadecenoic(elaidic), cis-11-octadecenoic, trans-11-octadecenoic (vaccenic),cis-5-eicosenoic, cis-9-eicosenoic (gadoleic), cis-11-docosenoic(cetoleic), cis-13-docosenoic (erucic), trans-13-docosenoic (brassidic),cis-15-tetracosenoic (selacholeic), cis-17-hexacosenoic (ximenic), andcis-21-triacontenoic (lumequeic) acids, as well as 2,4-hexadienoic(sorbic), cis-9-cis-12-octadecadienoic (linoleic),cis-9-cis-12-cis-15-octadecatrienoic (linolenic), eleostearic,12-hydroxy-cis-9-octadecenoic (ricinoleic), and like acids. Oleic acidis most preferred. Unsaturated fatty acids can be obtained commerciallyor synthesized by saponifying fatty acid esters, this method being knownto those in the art.

Fatty acid esters are formed by condensation of a fatty acid and analcohol. Fatty acid alkyl esters are fatty acids where the hydrogen ofthe —OH of the acid group is replaced by a hydrocarbyl group, typicallya C₁ to C₃₀ alkyl group, preferably a C₁ to C₂₀ alkyl.

Fatty acid alkyl esters are fatty acids where the hydrogen of the —OH ofthe acid group is replaced by an alkyl group. Fatty acid alkyl estersuseful herein are typically represented by the formula: R^—C(O)—O—R*,where R^ is a C₁ to C₁₀₀ hydrocarbyl group, preferably a C₆ to C₂₂group, preferably a C₆ to C₁₄ 1-alkene group, and R* is an alkyl group,preferably a C₁ to C₂₀ alkyl group, preferably methyl, ethyl, butyl,pentyl and hexyl. Preferred fatty acid alkyl esters useful herein aretypically represented by the formula: R^—CH₂═CH₂—R^—C(O)—O—R*, whereeach R^ is, independently a C₁ to C₁₀₀ alkyl group, preferably a C₆ toC₂₀, preferably a C₈ to C₁₄ alkyl group, preferably a C₉ group and R* isan alkyl group, preferably a C₁ to C₂₀ alkyl group, preferably methyl,ethyl, butyl, pentyl and hexyl. Particularly preferred fatty acid alkylesters useful herein are represented by the formula:CH₃—(CH₂)n-C═C—(CH₂)m-C(O)—O—R*,where and R* is an alkyl group, preferably a C1 to C20 alkyl group,preferably methyl, ethyl, butyl pentyl and hexyl, m and n are,independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 16,preferably 5, 7, 9 or 11, preferably 7.

Fatty acid methyl esters are fatty acids where the hydrogen of the —OHof the acid group is replaced by methyl group. Fatty acid methyl estersuseful herein are typically represented by the formula: R^—C(O)—O—CH₃,where R^ is a C₁ to C₁₀₀ hydrocarbyl group, preferably a C₆ to C₂₂group, preferably a C₆ to C₁₄ 1-alkene group. Preferred fatty acidmethyl esters useful herein are typically represented by the formula:R^—CH₂═CH₂—R^—C(O)—O—CH₃, where each R^ is, independently a C₁ to C₁₀₀alkyl group, preferably a C₆ to C₂₀, preferably a C₈ to C₁₄ alkyl group,preferably a C₉ group. Particularly preferred fatty acid methyl estersuseful herein are represented by the formula:CH₃—(CH₂)n-C═C—(CH₂)m-C(O)—O—CH₃, where m and n are, independently 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, preferably 5, 7, 9 or11, preferably 7.

Preferred fatty acid methyl esters include methyl palmitoleate, methyloleate, methyl gadoleate, methyl erucate, methyl linoleate, methyllinolenate, methyl soyate, and mixtures of methyl esters derived fromsoybean oil, beef tallow, tall oil, animal fats, waste oils/greases,rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleicsoybean oil (e.g., 75 mole % or more, preferably 85 mole % or more,preferably 90 mole % or more), high-oleic safflower oil (e.g., 75 mole %or more, preferably 85 mole % or more, preferably 90 mole % or more),high-oleic sunflower oil (e.g., 75 mole % or more, preferably 85 mole %or more, preferably 90 mole % or more), and other plant or animalderived sources containing fatty acids.

A preferred source of fatty acid methyl esters for use herein includesTAG's and biodiesel sources. As described above, biodiesel refers to atransesterified vegetable oil or animal fat based diesel fuel containinglong-chain alkyl (typically methyl, propyl, or ethyl) esters. Biodieselis typically made by chemically reacting lipids (such as vegetable oil)with an alcohol. Biodiesel, TAG's and derivatives thereof may be used inthe processes described herein. Likewise, preferred fatty acid methylesters useful herein may be obtained by reacting canola oil, corn oil,soybean oil, beef tallow, tall oil, animal fats, waste oils/greases,rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleicsoybean oil, high-oleic safflower oil, high-oleic sunflower oil ormixtures of animal and/or vegetable fats and oils with one or morealcohols (as described above), preferably methanol.

Vegetable oils useful herein preferably contain at least one site ofunsaturation and include, but are not limited to, canola, soybean, palm,peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed,linseed, safflower, pumpkin corn and other oils extracted from plantseeds.

For purposes of this invention and the claims thereto the term “feedoil” refers to one or more plant, animal or microbial oils, including,but not limited to, canola oil, corn oil, soybean oil, fish oil, beeftallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algaeoil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil,grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil,Jathropa oil, high-oleic soybean oil, high-oleic safflower oil,high-oleic sunflower oil, mixtures of animal and/or vegetable fats andoils, castor bean oil, dehydrated castor bean oil, cucumber oil,poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseedoil, meadowfoam, tuna oil, and sesame oils.

In a preferred embodiment, a combination of oils is used herein.Preferred combinations include two (three or four) or more of tall oil,palm oil, tallow, waste grease, rapeseed oil, canola oil, soy oil andalgae oil. Alternate useful combinations include two (three or four) ormore of soy oil, canola oil, rapeseed oil, algae oil, and tallow.

In certain embodiments processed oils, such as blown oils, are thesource of fatty acids useful herein. While vegetable oils are preferredsources of fatty acids for practicing disclosed embodiments of thepresent process, fatty acids also are available from animal fatsincluding, without limitation, lard and fish oils, such as sardine oiland herring oil, and the like. As noted above, in certain embodiments adesired fatty acid or fatty acid precursor is produced by a plant oranimal found in nature. However, particular fatty acids or fatty acidprecursors are advantageously available from genetically modifiedorganisms, such as genetically modified plants, particularly geneticallymodified algae. Such genetically modified organisms are designed toproduce a desired fatty acid or fatty acid precursor biosynthetically orto produce increased amounts of such compounds.

Alkyl oleates and alkyl erucates are fatty acid esters that are oftenmajor components in biodiesel produced by the transesterification ofalcohol and vegetable oils (preferably the alkyls are a C₁ to C₃₀ alkylgroup, alternately a C₁ to C₂₀ alkyl group). Biodiesel compositions thatare particularly useful in this invention are those which have highconcentrations of alkyl oleate and alkyl erucate esters. These fattyacid esters preferably have one site of unsaturation such thatcross-metathesis with ethylene yields 1-decene as the coproduct.Biodiesel compositions that are particularly useful are those producedfrom vegetable oils such as canola, rapeseed oil, palm oil, and otherhigh oleate oil, high erucate oils. Particularly preferred vegetableoils include those having at least 50% (on a molar basis) combined oleicand erucic fatty acid chains of all fatty acid chains, preferably 60%,preferably 70%, preferably 80%, preferably 90%.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) alkyl oleate fattyacid esters, preferably 60% of alkyl oleate fatty acid esters,preferably 70% of alkyl oleate fatty acid esters, preferably 80% ofalkyl oleate fatty acid esters, preferably 90% of alkyl oleate fattyacid esters.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) alkyl erucate fattyacid esters, preferably 60% of alkyl erucate fatty acid esters,preferably 70% of alkyl erucate fatty acid esters, preferably 80% ofalkyl erucate fatty acid esters, preferably 90% of alkyl erucate fattyacid esters.

In another embodiment, useful fatty acid ester containing mixturesinclude those having at least 50% (on a molar basis) combined oleic anderucic fatty acid esters of all fatty acid ester chains, preferably 60%,preferably 70%, preferably 80%, preferably 90%.

Isomerization

In another embodiment, the feed material is first isomerized, thencombined with a metathesis catalyst as described herein. For example,the processes disclosed herein may comprise providing a feed material(typically a fatty acid or fatty acid derivative), isomerizing a site ofunsaturation in the feed material (typically a fatty acid or fatty acidderivative) to produce an isomerized feed material (typically a fattyacid or fatty acid derivative), and then contacting the isomerizedmaterial with an alkene in the presence of a metathesis catalyst. Theisomerized material can be produced by isomerization with or withoutsubsequent esterification or transesterification. Isomerization can becatalyzed by known biochemical or chemical techniques. For example, anisomerase enzyme, such as a linoleate isomerase, can be used toisomerize linoleic acid from the cis 9, c is 12 isomer to the cis 9,trans 11 isomer. This isomerization process is stereospecific; however,nonstereospecific processes can be used because both cis and transisomers are suitable for metathesis. For example, an alternative processemploys a chemical isomerization catalyst, such as an acidic or basiccatalyst, can be used to isomerize an unsaturated feed material(typically a fatty acid or fatty acid derivative) having a site ofunsaturation at one location in the molecule into an isomerized, feedmaterial (typically a fatty acid or fatty acid derivative) having a siteof unsaturation at a different location in the molecule. Metal ororganometallic catalysts also can be used to isomerize an unsaturatedfeed material (typically a fatty acid or fatty acid derivative). Forexample, nickel catalysts are known to catalyze positional isomerizationof unsaturated sites in fatty acid derivatives. Similarly,esterification, transesterification, reduction, oxidation and/or othermodifications of the starting compound or products, such as a fatty acidor fatty acid derivative, can be catalyzed by biochemical or chemicaltechniques. For example, a fatty acid or fatty acid derivative can bemodified by a lipase, esterase, reductase or other enzyme before orafter isomerization. In another embodiment the isomerization describedabove may be practiced with any triacylglycerides, biodiesel, fattyacids, fatty acid esters and/or fatty acid alkyl esters describedherein, typically before contacting with the metathesis catalyst.

Metathesis Catalyst Compounds

In a preferred embodiment, the metathesis catalyst compound isrepresented by the Formula (I):

where:

-   M is a Group 8 metal, preferably Ru or Os, preferably Ru;-   X and X¹ are, independently, any anionic ligand, preferably a halide    (preferably Cl), an alkoxide, aryloxide, or an alkyl sulfonate, or X    and X¹ may be joined to form a dianionic group and may form single    ring of up to 30 non-hydrogen atoms or a multinuclear ring system of    up to 30 non-hydrogen atoms;-   L is a neutral two electron donor, preferably a phosphine or an    N-heterocyclic carbene or a cyclic alkyl amino carbene;-   L¹ is a heteroatom selected from the group consisting of N, O, P, or    S, preferably N or O;-   L and X may be joined to form a multidentate monoanionic group and    may form single ring of up to 30 non-hydrogen atoms or a    multinuclear ring system of up to 30 non-hydrogen atoms;-   R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substituted hydrocarbyl;-   G* is selected from the group consisting of hydrogen, a C₁ to C₃₀    hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl, preferably an    alkyl or substituted alkyl or hydrogen, preferably fluorinated    alkyls or hydrogen;-   R¹ is selected from the group consisting of hydrogen, a C₁ to C₃₀    hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl, preferably    methoxy- substituted phenyl, preferably 3,5- substituted phenyl,    preferably 3,5-dimethoxyphenyl; and-   each G is, independently, selected from the group consisting of    hydrogen, halogen, a C₁ to C₃₀ hydrocarbyl, and a C₁ to C₃₀    substituted hydrocarbyl hydrogen, (preferably a C₁ to C₃₀ alkyl or a    substituted C₁ to C₃₀ alkyl, or a C₅ to C₃₀ aryl or a substituted C₅    to C₃₀ aryl).

For purposes of this invention and claims thereto, a “Group 8 metal” isan element from Group 8 of the Periodic Table, as referenced by theIUPAC in Nomenclature of Inorganic Chemistry: Recommendations 1990, G.J. Leigh, Editor, Blackwell Scientific Publications, 1990.

For purposes of this invention and claims thereto a substitutedhydrocarbyl is a radical made of carbon and hydrogen where at least onehydrogen is replaced by a heteroatom. For purposes of this invention andclaims thereto a substituted alkyl or aryl group is a radical made ofcarbon and hydrogen where at least one hydrogen is replaced by aheteroatom or a linear, branched, or cyclic substituted or unsubstitutedhydrocarbyl group having 1 to 30 carbon atoms.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain or branched. Preferred alkoxides include a C₁ toC₁₀ alkyl group, preferably methyl, ethyl, propyl, butyl, or isopropyl.Preferred alkoxides include those where the alkyl group is a phenol,substituted phenol (where the phenol may be substituted with up to 1, 2,3, 4 or 5 C₁ to C₁₂ hydrocarbyl groups) or a C₁ to C₁₀ hydrocarbyl,preferably a C₁ to C₁₀ alkyl group, preferably methyl, ethyl, propyl,butyl, or phenyl.

Preferred alkyl sulfonates are represented by the Formula (II):

where R² is a C₁ to C₃₀ hydrocarbyl group, fluoro-substituted carbylgroup, chloro-substituted carbyl group, aryl group, or substituted arylgroup, preferably a C₁ to C₁₂ alkyl or aryl group, preferablytrifluoromethyl, methyl, phenyl, para-methyl-phenyl.

For purposes of this invention and claims thereto, “aryloxides” includethose where the aryl group is a phenol or naphthalene, or substitutedphenol or substituted naphthalene, where the phenol or naphthalene maybe substituted with one or more substituents. (Substituted meaning thata hydrogen group is replaced by a heteroatom or by a linear, branched,or cyclic hydrocarbyl group having 1 to 30 carbon atoms.) Suitablesubstituents are independently selected and may comprise halogen, C₁ toC₁₂ hydrocarbyl groups, substituted C₁ to C₁₂ hydrocarbyl groups,preferably halogen, trifluoromethyl, amino, alkyl, alkoxy,alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy,carboxyl, alkoxycarbonyl, aminocarbonyl, alkyaminocarbonyl,dialkylaminocarbonyl, hydroxy, nitro and the like, more preferablyphenyl, chlorophenyl, trifluoromethylphenyl, chlorofluorophenyl,aminophenyl, methylcarbonylphenyl, methoxyphenyl, methylendioxyphenyl,1-naphthyl and 2-naphthyl.

For purposes of this invention and claims thereto, “phosphines” may berepresented by the formula PR₃, wherein R is independently selected fromthe group comprising hydrogen, C₁ to C₁₂ hydrocarbyl groups, substitutedC₁ to C₁₂ hydrocarbyl groups, and halides.

For purposes of this invention and claims thereto, “N-heterocycliccarbenes” (NHCs) are represented by the Formula (III):

wherein the ring A is a 4-, 5-, 6-, or 7-membered ring, and Q is alinking group comprising from one to four linked vertex atoms selectedfrom the group comprising C, O, N, B, Al, P, S and Si with availablevalences optionally occupied by hydrogen, oxo or R— substituents,wherein R is independently selected from the group comprising C₁ to C₁₂hydrocarbyl groups, substituted C₁ to C₁₂ hydrocarbyl groups, andhalides, and each R⁴ is independently a hydrocarbyl group or substitutedhydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl,propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl,hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluoyl, chlorophenyl,phenol, or substituted phenol.

Some particularly useful N-heterocyclic carbenes may be represented bythe Formula (IV) and (V):

where

-   each R⁴ is independently a hydrocarbyl group or substituted    hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl,    ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl,    cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl,    cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl,    benzyl, toluoyl, chlorophenyl, phenol, substituted phenol, or    CH₂C(CH₃)₃; and-   each R⁵ is independently a hydrogen, a halogen, a C₁ to C₁₂    hydrocarbyl group, or a C₁ to C₁₂ substituted hydrocarbyl group,    preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl,    butyl, or aryl.

In other useful embodiments, one of the N groups bound to the carbene inFormulae (IV) or (V) is replaced with another heteroatom, preferably S,O or P, preferably an S heteroatom. Other useful N-heterocyclic carbenesinclude the compounds described in Hermann, W. A. Chem. Eur. J. 1996, 2,772 and 1627; Enders, D. et al., Angew. Chem. Int. Ed. 1995, 34, 1021;Alder R. W., Angew. Chem. Int. Ed. 1996, 35, 1121; and Bertrand, G. etal., Chem. Rev. 2000, 100, 39.

For purposes of this invention and claims thereto, “cyclic alkyl aminocarbenes” (CAACs) are represented by the Formula (VI):

wherein the ring A is a 4-, 5-, 6-, or 7-membered ring, and Q is alinking group comprising from one to four linked vertex atoms selectedfrom the group comprising C, O, N, B, Al, P, S and Si with availablevalences optionally occupied by hydrogen, oxo or R— substituents,wherein R is independently selected from the group comprising C₁ to C₁₂hydrocarbyl groups, substituted C₁ to C₁₂ hydrocarbyl groups, andhalides, and each R⁴ is independently a hydrocarbyl group or substitutedhydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl,propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl,hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl,cyclododecyl, mesityl, adamantyl, phenyl, benzyl, toluoyl, chlorophenyl,phenol, or substituted phenol.

Some particularly useful CAACs include:

Other useful CAACs include the compounds described in U.S. Pat. No.7,312,331 and Bertrand et al, Angew. Chem. Int. Ed. 2005, 44, 7236-7239.

Some preferred metathesis catalyst compounds include:

Although the catalyst compounds herein are described with respect toolefin cross-metathesis, one of skill in the art will appreciate thatthe catalyst compounds of this invention may be suitable for anymetathesis reaction, including but not limited to, ring-closingmetathesis, enyne metathesis, acyclic diene metathesis, and so on.

In certain embodiments, the catalyst compound employed in the process ofthis invention may be bound to or deposited on a solid catalyst support.The solid catalyst support will render the catalyst compoundheterogeneous, which will simplify catalyst recovery. In addition, thecatalyst support may increase catalyst strength and attritionresistance. Suitable catalyst supports include, without limitation,silicas, aluminas, silica-aluminas, aluminosilicates, including zeolitesand other crystalline porousaluminosilicates; as well as titanias,zirconia, magnesium oxide, carbon, and cross-linked, reticular polymericresins, such as functionalized cross-linked polystyrenes, e.g.,chloromethyl-functionalized cross-linked polystyrenes. The catalystcompound may be deposited onto the support by any method known to thoseskilled in the art, including, for example, impregnation, ion-exchange,deposition-precipitation, and vapor deposition. Alternatively, thecatalyst compound may be chemically bound to the support via one or morecovalent chemical bonds, for example, the catalyst compound may beimmobilized by one or more covalent bonds with one or more ofsubstituents of the indenylene ligand.

If a catalyst support is used, the catalyst compound may be loaded ontothe catalyst support in any amount, provided that the metathesis processof this invention proceeds to the desired metathesis products.Generally, the catalyst compound is loaded onto the support in an amountthat is greater than about 0.01 wt % of the Group 8 metal, andpreferably greater than about 0.05 wt % of the Group 8 metal, based onthe total weight of the catalyst compound plus support. Generally, thecatalyst compound is loaded onto the support in an amount that is lessthan about 20 wt % of the Group 8 metal, and preferably less than about10 wt % of the Group 8 metal, based on the total weight of the catalystcompound and support.

Synthesis of Metathesis Catalyst Compounds

The catalyst compounds described herein may be synthesized by anymethods known to those skilled in the art.

Representative methods of synthesizing the Group 8 catalyst compound ofthe type described herein include, for example, treating a solution ofthe ligand complex in a suitable solvent, such as THF, with a reactantcomplex of a Group 8 metal, such asdichloro-bis-(triphenylphosphine)ruthenium (II) and acetyl chloride. Themixture may be heated, for example to reflux, for a time periodappropriate to yield the desired chelating indenylene catalyst compound.Typically, removal of the volatiles affords the Group 8 chelatingindenylene catalyst compound, which may optionally be purified bysuitable chromatographical methods, as known in the art.

A phosphine ligand, such as tricyclohexylphosphine may be addedthereafter, if desired. The reaction conditions typically include mixingthe Group 8 reactant catalyst compound and the preferred phosphineligand in a suitable solvent, such as benzene, for a time sufficient toeffectuate the phosphine ligand exchange, at a suitable temperaturetypically ambient. Copper (I) chloride is then added in excess andremoval of the volatiles from resultant slurry typically affords theGroup 8 chelating indenylene catalyst compound comprising the morepreferred phosphine ligand.

While the present invention describes a variety of transition metalcomplexes useful in catalyzing metathesis reactions, it should be notedthat such complexes may be formed in situ. Accordingly, additionalligands may be added to a reaction solution as separate compounds, ormay be complexed to the metal center to form a metal-ligand complexprior to introduction to the reaction.

Alpha-Olefin Products of the Metathesis Reaction.

In a preferred embodiment, the processes described herein produce analpha olefin, preferably a linear alpha-olefin, which contains at leastone more carbon than the alkene used in the reaction to make thealpha-olefin.

In another embodiment, the processes described herein produce a blend ofan alpha olefin and an ester-functionalized alpha olefin. Generally amixture of non-ester-containing alpha olefins will be produced due tothe presence of mono-, di-, and tri-unsubstituted fatty acid chains. Themajor alpha olefin products are typically 1-decene, 1-heptene, and1-butene. The major ester-containing alpha olefin product is typicallymethyl 9-decenoate.

In a preferred embodiment, the alpha olefin produced herein is 1-decene.Typically the co-product of 1-decene is an ester.

In a preferred embodiment, the major alpha olefin produced herein is1-decene. Typically the coproduct of 1-decene is an ester.

In a preferred embodiment, ethylene and methyl oleate are combined withthe metathesis catalysts described herein (such astriphenylphosphinedichlorideruthenium(3-(3,5-dimethoxyphenyl)-6,8-dimethoxyinden-1-ylidene);triphenylphosphinedichlorideruthenium(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene);and/or tricyclohexylphosphinedichlorideruthenium(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene)) to produce1-decene and methyl 9-decenoate.

Separation of the 1-olefin (such as the 1-decene) from the ester may beby means typically known in the art such as distillation or filtration.

The linear alpha-olefin cross-metathesis product (such as 1-decene or amixture of C₈, C₁₀, C₁₂ linear alpha olefins) is then separated from anyesters present and preferably used to make poly-alpha-olefins(PAOs).Specifically, PAOs may be produced by the polymerization of olefin feedin the presence of a catalyst such as AlCl₃, BF₃, or BF₃ complexes.Processes for the production of PAOs are disclosed, for example, in thefollowing patents: U.S. Pat. Nos. 3,149,178; 3,382,291; 3,742,082;3,769,363; 3,780,128; 4,172,855; and 4,956,122, which are fullyincorporated by reference. PAOs are also discussed in Will, J. G.Lubrication Fundamentals, Marcel Dekker: New York, 1980. Certain highviscosity index PAO's may also be conveniently made by thepolymerization of an alpha-olefin in the presence of a polymerizationcatalyst such as Friedel-Crafts catalysts. These include, for example,aluminum trichloride, boron trifluoride, aluminum trichloride or borontrifluoride promoted with water, with alcohols such as ethanol,propanol, or butanol, with carboxylic acids, or with esters such asethyl acetate or ethyl propionate or ether such as diethyl ether,diisopropyl ether, etc., see for example, the methods disclosed by U.S.Pat. Nos. 4,149,178; 3,382,29; 3,742,082; 3,769,363 (Brennan); U.S. Pat.Nos. 3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355;4,956,122; 5,068,487; 4,827,073; 4,827,064; 4,967,032; 4,926,004; and4,914,254. PAO's can also be made using various metallocene catalystsystems. Examples include U.S. Pat. Nos. 6,706,828; 5,688,887;6,043,401; 6,548,724; 5,087,788; 6,414,090; 6,414,091; 4,704,491;6,133,209; 6,713,438; WO 96/23751; WO 03/020856; and EP 0 613 873.

PAOs are often used as additives and base stocks for lubricants, amongother things. Additional information on the use of PAO's in theformulations of full synthetic, semi-synthetic or part syntheticlubricant or functional fluids can be found in “Synthetic Lubricants andHigh-Performance Functional Fluids”, 2nd Ed. L. Rudnick, etc. MarcelDekker, Inc., N.Y. (1999). Additional information on additives used inproduct formulation can be found in “Lubricants and Lubrications, Ed. ByT. Mang and W. Dresel, by Wiley-VCH GmbH, Weinheim 2001.

In another embodiment this invention relates to:

-   1. A metathesis catalyst compound represented by the formula:

-   wherein M is a Group 8 metal; X and X¹ are anionic ligands; L is a    neutral two electron donor; L¹ is N, O, P, or S, preferably N or O;    R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substituted hydrocarbyl;    G* is selected from the group consisting of hydrogen, a C₁ to C₃₀    hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ is selected    from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl, and    a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selected    from the group consisting of hydrogen, halogen, C₁ to C₃₀    hydrocarbyls and C₁ to C₃₀ substituted hydrocarbyls, preferably the    compound comprises one or more of:    triphenylphosphinedichlorideruthenium(3-(3,5-dimethoxyphenyl)-6,8-dimethoxyinden-1-ylidene);    triphenylphosphinedichlorideruthenium(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene);    tricyclohexylphosphinedichlorideruthenium    (3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene); or mixtures    thereof.-   2. The catalyst compound of paragraph 1, wherein M is Ru.-   3. The catalyst compound of paragraph 1 or 2, wherein X and X¹ are,    independently, a halogen, an alkoxide, aryloxide, or an alkyl    sulfonate.-   4. The catalyst compound of any of paragraphs 1 to 3, wherein at    least of X and X¹ is chloride, preferably both X and X¹ are    chloride.-   5. The catalyst compound of any of paragraphs 1 to 4, wherein L¹ is    N or O.-   6. The catalyst compound of any of paragraphs 1 to 5, wherein L is    selected from the group consisting of a phosphine, an N-heterocyclic    carbene, and a cyclic alkyl amino carbene.-   7. The catalyst compound of any of paragraphs 1 to 6, wherein G* is    selected from the group consisting of hydrogen, an alkyl, and    substituted alkyl.-   8. The catalyst compound of any of paragraphs 1 to 7, wherein each G    is independently, a C₁ to C₃₀ substituted or unsubstituted alkyl, or    a substituted or unsubstituted C₄ to C₃₀ aryl.-   9. The catalyst compound of any of paragraphs 1 to 8, wherein R¹ is    a methoxy substituted phenyl.-   10. The catalyst compound of any of paragraphs 1 to 9, wherein L and    X are joined to form a multidentate monoanionic group or a dianionic    group and may form a single ring of up to 30 non-hydrogen atoms or a    multinuclear ring system of up to 30 non-hydrogen atoms.-   11. A process to produce alpha-olefin comprising contacting a feed    material (such as a feed oil) with the catalyst compound of any of    paragraphs 1 to 10.-   12. The process of paragraph 11, wherein the feed material is    selected from the group consisting of canola oil, corn oil, soybean    oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower    oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower    oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil,    high-oleic safflower oil, high-oleic sunflower oil, mixtures of    animal and vegetable fats and oils, castor bean oil, dehydrated    castor bean oil, cucumber oil, poppyseed oil, flaxseed oil,    lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil,    sesame oils and mixtures thereof.-   13. The process of paragraph 11, wherein the feed material is    selected from the group consisting of palm oil and algae oil.-   14. A process to produce alpha-olefin comprising contacting a    triacylglyceride with an alkene and the catalyst compound of any of    paragraphs 1 to 10, preferably wherein the alpha olefin produced has    at least one more carbon atom than the alkene.-   15. The process of paragraph 14, wherein the triacylglyceride is    contacted with alcohol and converted to a fatty acid ester or fatty    acid alkyl ester prior to contacting with the catalyst compound of    any of paragraphs 1 to 10.-   16. The process of paragraph 14, wherein the triacylglyceride is    contacted with water or an alkaline reagent and converted to a fatty    acid prior to contacting with the catalyst compound of any of    paragraphs 1 to 10.-   17. A process to produce alpha-olefin comprising contacting an    unsaturated fatty acid with an alkene and the catalyst compound of    any of paragraphs 1 to 10, preferably wherein the alpha olefin    produced has at least one more carbon atom than the alkene.-   18. A process to produce alpha-olefin comprising contacting a    triacylglyceride with the catalyst compound of any of paragraphs 1    to 10, preferably wherein the alpha olefin produced has at least one    more carbon atom than the alkene.-   19. A process to produce alpha-olefin comprising contacting an    unsaturated fatty acid ester and or unsaturated fatty acid alkyl    ester with an alkene and the catalyst compound of any of paragraphs    1 to 10, preferably wherein the alpha olefin produced has at least    one more carbon atom than the alkene.-   20. The process of any of paragraphs 11 to 19, wherein the alpha    olefin is a linear alpha-olefin having 4 to 24 carbon atoms.-   21. The process of any of paragraphs 11 to 20, wherein the alkene is    ethylene, propylene, butene, hexene or octene.-   22. The process of any of paragraphs 19 to 21, where the fatty acid    ester is a fatty acid methyl ester.-   23. The process of any of paragraphs 14 to 22, wherein the    triacylglyceride, fatty acid, fatty acid alkyl ester, fatty acid    ester is derived from biodiesel.-   24. The process of any of paragraphs 11 to 23, wherein the    alpha-olefin is butene-1, decene-1 and or heptene-1.-   25. The process of any of paragraphs 11 to 24, wherein the    productivity of the process is at least 200 g of linear alpha-olefin    per mmol of catalyst per hour.-   26. The process of any of paragraphs 11 to 25, wherein the    selectivity of the process is at least 20 wt % linear alpha-olefin,    based upon the weight to the material exiting the reactor.-   27. The process of any of paragraphs 11 to 26, wherein the turnover    number, defined as the moles of alpha olefin formed per mol of    catalyst, of the process is at least 10,000.-   28. The process of any of paragraphs 11 to 27, wherein the yield,    when converting unsaturated fatty acids, unsaturated fatty acid    esters, unsaturated fatty acid alkyl esters or mixtures thereof, is    30% or more, said yield being defined as the moles of alpha olefin    formed per mol of unsaturated fatty acids, unsaturated fatty acid    esters, unsaturated fatty acid alkyl esters or mixtures thereof    introduced into the reactor.-   29. The process of any of paragraphs 11 to 27, wherein the yield,    when converting TAGs as represented in the formula below, is 30% or    more, said yield being defined as the moles of alpha olefin formed    divided by (the moles of unsaturated R^(a)+moles of unsaturated    R^(b)+moles of unsaturated R^(c)) introduced into the reactor,

-   where R^(a), R^(b) and R^(c) each, independently, represent a    saturated or unsaturated hydrocarbon chain.-   30. The process of paragraph 28, wherein the yield is 60% or more.-   31. A process to produce C₄ to C₂₄ linear alpha-olefin comprising    contacting a feed material with an alkene selected from the group    consisting of ethylene, propylene butene, pentene, hexene, heptene,    octene, nonene and mixtures thereof and a metathesis catalyst    compound of any of paragraphs 1 to 10, wherein the feed material is    a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty    acid ester derived from seed oil.-   32. The process of claim 31, wherein the alkene is ethylene, the    alpha olefin is 1-butene, 1-heptene and or -decene, and the feed    material is a fatty acid methyl ester, and/or fatty acid ester.

EXPERIMENTAL SECTION

For purposes of this invention and the claims thereto, Et is ethyl, Meis methyl, Ph is phenyl, Cy is cyclohexyl, THF is tetrahydrofuran, AcClis acetyl chloride, DMF is dimethylformamide, and TLC is thin layerchromatography.

Typical dry-box procedures for synthesis of air-sensitive compounds werefollowed including using dried glassware (90° C., 4 hours) and anhydroussolvents purchased from Sigma Aldrich (St. Louis, Mo.) which werefurther dried over 3 A sieves. All reagents were purchased fromSigma-Aldrich, unless otherwise noted. ¹H, ¹³C, and ³¹P spectra wererecorded on Bruker 250 and 500 spectrometers. IR data was recorded onBruker Tensor 27 FT-IR spectrometer. Yields of metathesis product andcatalyst turnover numbers were calculated from data recorded on anAgilent 6890 GC spectrometer as shown below.

Typically, a sample of the metathesis product will be taken and analyzedby GC. An internal standard, usually tetradecane, is used to derive theamount of metathesis product that is obtained. The amount of metathesisproduct is calculated from the area under the desired peak on the GCtrace, relative to the internal standard.

Yield is reported as a percentage and defined as 100×[micromoles ofmetathesis products obtained by GC]/[micromoles of feed material weighedinto reactor]. Selectivity is reported as a percentage and is defined as100×[area under the peak of desired metathesis products]/[sum of peakareas of cross-metathesis and the homometathesis products]. Catalystturnovers for production of the metathesis products is defined as the[micromoles of metathesis product]/([micromoles of catalyst].

In a particular embodiment, the metathesis of methyl oleate withethylene will yield co-metathesis products of 1-decene andmethyl-9-decenoate. In addition to the desired products, the methyloleate may homometathesize to produce small amounts of 9-octadecene, aless desirable product, and 1,18-dimethyl-9-octadecenedioate, a secondless desirable product. Yield is defined as 100×[micromoles ofethenolysis products obtained from the GC]/[micromoles of methyl oleateweighed into reactor]. 1-decene selectivity is shown as a percentage andis defined as 100×[GC peak area of 1-decene & methyl-9-decenoate]/[sumof GC peak areas of 1-decene, methyl-9-decenoate, and the homometathesisproducts, 9-octadecene, and 1,18-dimethyl-9-octadecenedioate]. Catalystturnovers for production of the 1-decene is defined as the [micromolesof 1-decene obtained from the GC]/([micromoles of catalyst].

EXAMPLES

Synthetic protocols for representative alkylidene ligands and thecorresponding ruthenium alkylidene complexes are as follows. Otheralkylidene ligands and their respective metal complexes may be derivedanalogously.

Example 1 Synthesis of(PPh₃)Cl₂Ru(3-3,5-dimethoxyphenyl-6,8-dimethoxyinden-1-ylidene)

Bis(3,5-dimethoxyphenyl)methanol (A): 3,5-Dimethoxybenzaldehyde (5.0 g,30 mmol) was dissolved in 150 mL THF in a 500 mL round bottom flask.3,5-Dimethoxyphenyl magnesium chloride (1 M in THF, 45 mL) was addedslowly. The reaction was heated at 40° C. for 4 hours, then quenchedwith saturated ammonium chloride. The mixture was extracted with 3portions of ether and the combined organic layers washed with brine,dried over anhydrous MgSO₄, then concentrated to a crude pale yellowsolid which was carried forward to the next step.: ¹H NMR (250 MHz,C₆D₆): δ 3.29 (d, J=5.0 Hz, 12H), 6.46 (m, 2H), 6.56 (m, 1H), 6.76 (m,2H), 7.04 (t, J=8.2 Hz, 1H).

Bis(3,5-dimethoxyphenyl)methanone (B): Pyridinium chlorochromate (PCC)(12.9 g, 30 mmol) was suspended in 30 mL dichloromethane in a 200 mLround bottom flask. Crude bis(3,5-dimethoxyphenyl)methanol from above(compound A) was suspended in 30 mL dichloromethane then added to thechromate suspension. The dark solution was allowed to stir at ambienttemperature for 18 hours then diluted with ether. After decantation, theorganic solution was washed twice with 1N NaOH, twice with 10% HCl,saturated NaHCO₃, and then with brine. It was dried over anhydrousMgSO₄, filtered and concentrated to give a brownish yellow solid. Thebrownish yellow solid was purified by column chromatography using 50%acetone/hexane as eluent giving the product as a yellow solid in 63%yield over 2 steps: IR (cm⁻¹): 2960, 2938, 2834, 1660, 1592, 1456, 1425,1349, 1304, 1205, 1157, 1066, 744; ¹H NMR (250 MHz, C₆D₆): δ 3.21 (s,12H), 6.67 (t, J=2.2 Hz, 2H), 7.21 (d, J=2.5 Hz, 4H); ¹³C NMR (63 MHz,C₆D₆): 54.9 (4C), 105.3 (2C), 108.0 (4C), 140.2 (2C), 161.1 (4C), 195.2.

1,1-Bis(3,5-dimethoxyphenyl)prop-2-yn-1-ol (C): In a 100 mL flask,bis(3,5-dimethoxy-phenyl)methanone (compound B, 1.2 g, 3.9 mmol) wasdissolved in 20 mL diethyl ether. Approximately 5 mL THF was added tohelp solvate the ketone followed by the slow addition ofethynylmagnesium bromide (0.5 M in THF, 12 mL). The reaction wasmonitored by TLC and upon consumption of starting material, 2N HCl wasadded to the flask. The mixture was extracted 3 times with ethyl acetateand the combined organic layers were washed with brine, dried overanhydrous MgSO₄, filtered, and concentrated to give a yellow oil.Purification was achieved with column chromatography using a gradient of30% to 50% acetone/hexane. The product was obtained as a pale yellow oilin 73% yield: R_(f) 0.14 (30:70 acetone/hexane); IR (cm⁻¹): 3441, 3280,2940, 2837, 1598, 1460, 1289, 1205, 1156, 1053, 834, 748, 689; ¹H NMR(250 MHz, C₆D₆): δ 2.38 (s, 1H), 2.94 (br s, 1H), 3.27 (s, 12H), 6.42(t, J=2.5 Hz, 2H), 3.99 (d, J=2.5 Hz, 4H); ¹³C NMR (63 MHz, C₆D₆): 54.8(4C), 74.5, 75.3, 86.8, 100.1 (2C), 104.9 (4C), 147.6 (2C), 161.2 (4C).

(PPh₃)Cl₂Ru(3-3,5-dimethoxyphenyl-6,8-dimethoxyinden-1-ylidene) (D):Acetyl chloride (5-10 μl) was added to a solution of (PPh₃)₃RuCl₂ (336mg, 0.35 mmol) and 1,1 di(3,5-dimethoxy)phenyl 2-propyn-1-ol (compoundC, 172 mg, 0.525 mmol) in 6 mL THF. The propynol was added as a 0.2 Msolution in THF. The solution was allowed to reflux for 18 hours, afterwhich the reaction flask was placed under high vacuum to remove thesolvent. Isopropanol (12 mL) was added to the reaction flask and thepurple material was removed from the walls by intense stiffingovernight. The resulting suspension was filtered and washed with 5 mL ofisopropanol followed by two pentane washes (5 mL each). Any remainingsolvent was removed from the red-brown powder in vacuo at 60° C.,yielding 240 mg (92%). The product was characterized by NMR spectra (¹H,¹³C, and ³¹P). The results are as below:

¹H NMR (250 MHz, CD₂Cl₂, 30° C.): δ=7.4 (bt, 11H), 6.0-7.0 (m, 6H), 4.57(s, 0.5H), 3.74-4.0 (m, 6H, R—OCH₃×2), 3.64 (s, 6H, R—OCH₃×2). ¹³C NMR(500 MHz, CD₂Cl₂, 30° C.): δ=289.7 (d, J_(PC)=100 Hz). ³¹P NMR (250 MHz,CD₂Cl₂, 30° C.): δ=54 ppm.

Example 2 Synthesis of(PPh₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene) (J)

Isopropyl 3,5-diisopropoxybenzoate (E): In a 1 L round bottom flask,3,5-dihydroxybenzoic acid (10 g, 64 mmol), potassium carbonate (42 g,260 mmol) and cesium carbonate (30 g, 92 mmol) were dissolved in 300 mLdimethylformamide. After stiffing at ambient temperature forapproximately 20 min, 2-iodopropane (43 g, 256 mmol) was added. Thereaction was allowed to stir overnight, then quenched with water andextracted with three portions of ethyl acetate. The combined organiclayers were washed twice with both water and brine, then dried (MgSO₄),filtered and concentrated to a yellow oil: R_(f) 0.48 (30:70acetone/hexane); IR (cm⁻¹): 2978, 2935, 1715, 1593, 1449, 1372, 1296,1234, 1183, 1112, 1038, 769; ¹H NMR (250 MHz, C₆D₆): δ 1.07 (dd, J=6.7,12.0 Hz, 18H), 4.20 (qn, J=6.2 Hz, 2H), 5.22 (qn, J=6.2 Hz, 1H), 6.75(t, J=2.5 Hz, 1H), 7.56 (d, J=2.5 Hz, 2H); ¹³C NMR (63 MHz, C₆D₆): 23.7(2C), 23.8 (4C), 70.2, 71.8 (2C), 110.9, 111.1 (2C), 135.5, 161.6 (2C),167.9.

3,5-diisopropoxybenzoic acid (F): Crude isopropoxybenzoate from above(compound E) was dissolved in 200 mL THF/H₂O (1:1) in a 500 mL flask.Excess lithium hydroxide (10 g) was added and the reaction refluxed forover 48 hours. The mixture was cooled, acidified with HCl to pH 2, thenextracted with several portions of diethyl ether. The organic layerswere washed with brine, dried over MgSO₄, and concentrated to a whitesolid in 55% yield over 2 steps: IR (cm⁻¹): 3064, 2978, 2933, 2639,1693, 1594, 1300, 1158, 1114, 1040, 767; ¹H NMR (250 MHz, CD₃OD): δ 1.30(dd, J=2.3, 5.9 Hz, 12H), 4.59 (qn, J=6.2 Hz, 2H), 6.61 (t, J=2.3 Hz,1H), 7.10 (d, J=2.5 Hz, 2H); ¹³C NMR (63 MHz, CD₃OD): 22.2 (4C), 71.2(2C), 109.8, 109.9, 133.8, 160.3 (2C), 169.7.

3,5-diisopropoxy-N-methoxy-N-methylbenzamide (G): Diisopropoxybenzoicacid (compound F, 10 g, 41 mmol) was dissolved in benzene (100 mL) in a500 mL round bottom flask. Thionyl chloride (12.2 mL, 168 mmol) wasadded and the reaction heated at reflux for 1 hour. The mixture was thencooled to room temperature and concentrated under reduced pressure. Theresulting residue was redissolved in dichloromethane and concentratedagain to give 3,5-diisopropoxybenzoyl chloride. In a separate 200 mLflask, N,O-dimethylhydroxylamine-HCl (4.0 g, 42 mmol) was suspended in80 mL dichloromethane at 0° C. Triethylamine (12.4 mL, 88 mmol) wasadded slowly, followed by crude 3,5-diisopropoxybenzoyl chloride. Thereaction flask was allowed to warm to ambient temperature and stirredovernight. The reaction was quenched with water and extracted with threeportions of dichloromethane. The combined organic layers were washedwith brine, dried over MgSO₄, filtered and concentrated under reducedpressure. Purification of the resulting brown oil by columnchromatography (30% acetone/hexane) gave the Weinreb amide (compound G)as a yellow oil in 60% yield from 3,5-dihydroxybenzoic acid: R_(f) 0.33(30:70 acetone/hexane); IR (cm⁻¹): 2977, 1647, 1590, 1441, 1374, 1184,1155, 1113, 1037, 964; ¹H NMR (250 MHz, C₆D₆): δ 1.06 (dd, J=2.5, 5.9Hz, 12H), 3.00 (s, 3H), 3.05 (s, 3H), 4.19 (qn, J=6.2 Hz, 2H), 6.69 (t,J=2.5 Hz, 1H), 7.10 (d, J=2.5 Hz, 2H); ¹³C NMR (63 MHz, C₆D₆): 21.9(4C), 33.4, 60.4, 69.8 (2C), 106.6, 108.1 (2C), 137.0, 159.3 (2C),169.8.

3,5-diisopropoxyphenylperfluorophenylmethanone (H): In a 200 mL roundbottom flask, the Weinreb amide (compound G, 1 g, 3.5 mmol) wasdissolved in ether and cooled. Pentafluorophenylmagnesium bromide (0.5 Min THF, 8.52 mL) was added slowly and the reaction stiffed under ambientconditions overnight. The mixture was quenched with saturated ammoniumchloride and extracted with three portions of ether. Combined organiclayers were washed with brine, dried over anhydrous MgSO₄, filtered andconcentrated to give a dark brown oil which upon column chromatography(40% acetone/hexane) crystallized to the desired ketone in 46% yield:R_(f) 0.60 (30:70 acetone/hexane); IR (cm⁻¹): 2980, 1682, 1588, 1501,1320, 1185, 1160, 1113, 991, 770; ¹H NMR (250 MHz, C₆D₆): δ 1.02 (d,J=5.0 Hz, 12H), 4.10 (qn, J=7.5 Hz, 2H), 6.66 (t, J=2.2 Hz, 1H), 7.13(d, J=2.2 Hz, 2H); ¹³C NMR (63 MHz, C₆D₆): 21.6 (4C), 70.2 (2C), 109.1(2C), 109.8, 138.5, 160.1 (2C), 184.9.

1-(3,5-diisopropoxyphenyl)-1-perfluorophenylprop-2-yn-1-ol (I): Theabove methanone (compound H, 3.2 g, 8.2 mmol) was dissolved in 40 mLether in a 100 mL round bottom flask. Ethynylmagnesium bromide (0.5 M inTHF, 24.6 mL) was added slowly and the reaction stirred overnight. Thereaction was quenched with saturated ammonium chloride and extractedwith three portions of ether. Combined organic layers were washed withbrine, dried over anhydrous MgSO₄, filtered and concentrated. Theresulting oil was purified by column chromatography (40% acetone/hexane)and gave the desired propargyl alcohol as a dark brown oil in 47% yield:R_(f) 0.15 (40:60 acetone/hexane); IR (cm⁻¹): 3423, 3309, 2979, 1595,1524, 1492, 1115, 985; ¹H NMR (250 MHz, C₆D₆): δ 1.10 (d, J=7.5 Hz,12H), 2.29 (s, 1H), 2.67 (s, 1H), 4.26 (qn, J=6.7 Hz, 2H), 6.54 (t,J=2.3 Hz, 1H), 7.11 (d, J=2.5 Hz, 2H); ¹³C NMR (63 MHz, C₆D₆): 21.9(4C), 69.8 (2C), 71.9, 75.7, 83.7, 103.6, 105.8 (2C), 145.2, 159.8 (2C).

(PPh₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene) (J): A100 mL flask was charged with 1-(3,5 diisopropoxyphenyl),1-(pentafluorophenyl)-2-propyn-1-ol (compound H, 503 mg, 1.2 mmol). THF(47 mL) was then added followed by Ru(PPh₃)₃Cl₂ (1.17 g, 1.2 mmol) andacetyl chloride (AcCl) (86 μL in 0.86 mL THF). The reaction was refluxedfor 1.5 hours after which all solvent was removed under a stream of N₂.The residue was suspended in 45 mL isopropanol with vigorous stirring at40° C. for 1 hour. The resulting suspension was filtered and washedthrice with isopropanol (20 mL each time) and dried in vacuo. The crudematerial was loaded onto a flash column dissolved in 50%hexane/dichloromethane, and eluted with 100% dichloromethane. Thesolvent was removed in vacuo yielding 240 mg (23%) of the desiredcompound. Additional crude material was eluted with 1% and 2% MeOH indichloromethane. This material contained PPh₃ and an unidentifieddecomposition product observed at 28.6 ppm in the ³¹P spectrum. Theproduct was characterized by NMR spectra (¹H, ¹³C, and ³¹P). The resultsare as below:

¹H NMR (500 MHz, CD₂Cl₂, 30° C.): δ=6.0-7.0 (m, 15H), 6.62 (s, 1H), 6.56(d, J=1 Hz, 1H), 6.50 (d, J=1.5 Hz, 1H), 5.17 (sept d, J=2, 6 Hz, 1H),4.61 (sept, J=6 Hz, 1H), 1.75 (d, J=6 Hz, 6H), 1.36 (d, J=6 Hz, 6H); ¹⁹FNMR (250 MHz, CD₂Cl₂, 30° C.): δ=−137.39 (d, J=17.5 Hz, 2F), −154.66 (t,J=22.5 Hz, 1F), −162.6 (dt, J=6.5, 22.5 Hz, 2F); ³¹P NMR (250 MHz,CD₂Cl₂, 30° C.): δ=63 ppm.

Example 3 Synthesis of(PCy₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene) (K)

(PCy₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene) (K): A10 mL vial was charged with(PPh₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene)(compound J, 0.40 grams). Benzene (2 mLs) was then added followed bytricyclohexylphosphine (0.13 grams). The reaction was allowed to sitovernight. Excess Cu(I)Cl was added, approximately 0.50 grams. Theresulting slurry was dried under vacuum, and pentane was used to extractthe product (0.038 g) from the solids. The product was characterized byNMR spectra (¹H, ¹³C and ³¹P). The results are as below: ¹H NMR (250MHz, CD₂Cl₂, 30° C.): δ=7.35 (s, 1H), 6.64 (s, 1H), 6.38 (s, 1H), 4.62(sept, 1H), 4.26 (sept, 1H), 1.72 (d, 6H), 1.36 (d, 6H), 1.5-2.4 (m,33H); ¹⁹F NMR (250 MHz, CD₂Cl₂, 30° C.): δ=−137.34 (d, J=17.5 Hz, 2F),−154.4 (t, J=22.5 Hz, 1F), −161.6 (dt, J=6.5, 22.5 Hz, 2F); ³¹P NMR (250MHz, CD₂Cl₂, 30° C.): δ=68 ppm.

X-ray Crystallography

X-ray quality crystals of these ruthenium complexes may be grown bydissolving the crude material in a minimal amount of a solvent such asdichloromethane and then adding an excess of another solvent ofdiffering polarity, for example, isopropanol or hexanes. This solutionis then allowed to evaporate at ambient temperature, usually under anitrogen atmosphere, to yield crystals of the desired ruthenium complex.The crystals are usually removed from the solvent by using a glass frit.Any solid isolated from the filtrate usually contains impure crystals.

For example, X-ray quality crystals of compound J, above, were grown bydissolving the crude material in a minimal amount of dichloromethane andadding a tenfold excess of isopropanol. This solution was allowed topartially evaporate overnight at ambient temperature under a N₂atmosphere to yield X-ray quality crystals.

Solid-state structure of CompoundJ[(PPh₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene)] asdetermined by single-crystal x-ray diffraction Key data and collectionparameters: RuC₃₉H₃₂PCl₂O₂F₅, FW 830.62, red-brown irregular,0.6×0.3×0.06 mm, orthorhombic, a=13.268 (1) A, b=20.385 (2) A, c=27.051(3) A, V=7316 (1) A³, Pbca (#61), Z=8, d_(calc)=1.508, mu=6.77 cm⁻¹, No.obs=8342, No. variables=452, R1 (I>2σ(I))=0.115, wR2 (allreflections)=0.1826, GOF=1.137, peak=0.61, hole=−0.49, maxshift/error=0.001.

Atomic coordinates and B_(iso)/B_(eq) Atom x y z B_(eq) Ru(1)−0.08116(5) 0.18381(3) 0.63755(2) 2.456(14) Cl(1) −0.17357(15)0.11104(11) 0.58978(8) 3.63(4) Cl(2) 0.00689(16) 0.20266(13) 0.70936(8)4.36(5) P(1) 0.05766(14) 0.17048(10) 0.59166(8) 2.65(3) F(1) −0.1092(4)0.4978(2) 0.6239(2) 5.44(12) F(2) −0.0824(4) 0.6051(2) 0.5668(2)5.95(13) F(3) −0.1069(4) 0.5980(2) 0.4677(2) 6.48(15) F(4) −0.1419(4)0.4794(2) 0.4239(2) 5.97(13) F(5) −0.1611(4) 0.3709(2) 0.48075(19)5.65(12) O(1) −0.2244(3) 0.2022(2) 0.68818(18) 2.93(10) O(2) −0.4318(5)0.4008(3) 0.7040(2) 5.67(16) C(1) 0.0825(5) 0.0832(4) 0.5833(3) 3.15(15)C(2) 0.0763(7) 0.0422(4) 0.6239(3) 5.2(2) C(3) 0.0899(9) −0.0244(5)0.6186(5) 7.2(3) C(4) 0.1106(8) −0.0518(5) 0.5723(6) 7.0(3) C(5)0.1178(7) −0.0110(5) 0.5325(4) 5.3(2) C(6) 0.1036(5) 0.0560(4) 0.5370(3)3.91(18) C(7) 0.1722(6) 0.2041(4) 0.6194(2) 3.38(17) C(8) 0.2554(6)0.1642(4) 0.6318(3) 4.30(19) C(9) 0.3388(6) 0.1911(7) 0.6542(3) 6.1(2)C(10) 0.3427(8) 0.2556(7) 0.6661(3) 6.9(3) C(11) 0.2631(8) 0.2957(6)0.6531(3) 6.5(2) C(12) 0.1787(6) 0.2691(5) 0.6304(3) 5.1(2) C(13)0.0577(6) 0.2029(3) 0.5293(2) 2.97(15) C(14) 0.1445(6) 0.2284(4)0.5075(3) 3.73(18) C(15) 0.1441(7) 0.2494(4) 0.4586(3) 4.7(2) C(16)0.0564(8) 0.2462(4) 0.4322(3) 4.8(2) C(17) −0.0298(7) 0.2228(4)0.4530(3) 4.4(2) C(18) −0.0304(6) 0.2011(4) 0.5013(3) 3.49(17) C(19)−0.1154(5) 0.2667(3) 0.6164(2) 2.51(14) C(20) −0.0863(5) 0.3180(3)0.5809(2) 2.84(14) C(21) −0.1466(5) 0.3714(3) 0.5859(2) 2.64(14) C(22)−0.2217(5) 0.3587(3) 0.6258(2) 2.93(15) C(23) −0.2006(5) 0.2955(3)0.6420(2) 2.36(13) C(24) −0.2988(5) 0.3940(4) 0.6473(2) 3.40(17) C(25)−0.3536(6) 0.3631(4) 0.6861(3) 3.70(18) C(26) −0.3333(6) 0.2997(4)0.7013(3) 3.29(16) C(27) −0.2563(6) 0.2657(3) 0.6786(2) 2.79(14) C(28)−0.1398(5) 0.4311(4) 0.5552(2) 2.84(15) C(29) −0.1208(6) 0.4924(4)0.5747(3) 3.60(17) C(30) −0.1081(6) 0.5485(4) 0.5462(4) 4.4(2) C(31)−0.1181(6) 0.5442(4) 0.4959(4) 4.5(2) C(32) −0.1360(6) 0.4848(4)0.4747(3) 3.82(18) C(33) −0.1448(6) 0.4293(4) 0.5033(3) 3.47(17) C(34)−0.3990(11) 0.4325(9) 0.7869(5) 13.4(6) C(35) −0.4645(9) 0.3920(5)0.7544(4) 6.0(2) C(36) −0.5695(9) 0.4154(7) 0.7577(4) 10.2(4) C(37)−0.2186(7) 0.1001(4) 0.7306(3) 4.6(2) C(38) −0.2857(5) 0.1582(4)0.7192(3) 3.23(16) C(39) −0.3794(6) 0.1380(4) 0.6904(3) 4.29(19) WhereB_(eq) = 8/3 π²(U₁₁(aa*)² + U₂₂(bb*)² + U₃₃(cc*)² + 2U₁₂(aa*bb*)cos γ +2U₁₃(aa*cc*)cos β + 2U₂₃(bb*cc*)cos α).Cross Metathesis Reactions

Representative experimental protocols for cross metathesis reactions arepresented in the examples below.

Example 4 Ethylenolysis of Methyl Oleate with Ethylene Using Compound D[triphenylphosphineruthenium(3-(3,5-dimethoxyphenyl)-5,7-dimethoxy-indenylidene)]

In a 120 mL bottle,triphenylphosphineruthenium(3-(3,5-dimethoxyphenyl)-5,7-dimethoxy-indenylidene)(compound D, 5.0 mg, 6.57 μmol) was combined with 100 mL dichloromethaneto make a stock solution. Some of this ruthenium catalyst compound stocksolution (3.8 mL, 250 nmol) was added to a 20 mL scintillation vialalong with 1 equivalent of tricyclohexylphosphine (250 nmol, added as asolution in dichloromethane). Tetradecane (0.152 g) was then added as astandard for gas chromatography analysis. The contents of the vial weretransferred to a 100 mL Fisher-Porter vessel equipped with a stirringbar which was then sealed and charged with ethylene (150 psi). Thebottle was then placed in an oil bath heated to 40° C. for 2 hours. Thebottle was depressurized, opened and a few drops (˜0.1 mL) of ethylvinyl ether were added prior to analysis. 1-Decene andmethyl-9-decenoate yields corresponded to 1800 turnovers of decene perequivalent of ruthenium.

Example 5 Ethylenolysis of Methyl Oleate Using Compound K,(PCy₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene)

The ethylenolysis of methyl oleate was used as a test to determine theactivity of(PCy₃)Cl₂Ru(3-pentafluorophenyl-6,8-diisopropoxyinden-1-ylidene). Acatalyst compound stock solution (0.1379 mM) was made by dissolving thecatalyst compound in anhydrous dichloromethane. Methyl oleate (0.87 g,1.0 mL), catalyst compound stock solution (0.906 g), dichloromethane(4.12 g), and tetradecane (0.152 g) as an internal standard were placedin a Fisher-Porter bottle equipped with a stir bar. The vessel was thenfilled with ethylene to 150 psig and placed in an oil bath heated to 40°C. for 3 hours. The vessel was then depressurized and 5 drops ethylvinyl ether added to stop the reaction. A sample was analyzed by gaschromatography. The cross-metathesis reaction yielded 18.5% 1-decene andmethyl-9-decenoate with 99% selectivity 1-Decene and methyl-9-decenoateyields corresponded to 4300 turnovers of decene per equivalent ofruthenium.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications may be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

1. A catalyst compound for the metathesis of olefins represented by theformula:

wherein M is a Group 8 metal from the Periodic Table of the Elements; Xand X¹ are anionic ligands; L is a neutral two electron donor; L¹ is Oor S; R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substitutedhydrocarbyl; G* is selected from the group consisting of hydrogen, a C₁to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ isselected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl,and a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selectedfrom the group consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbylsand C₁ to C₃₀ substituted hydrocarbyls.
 2. The catalyst compound ofclaim 1, wherein M is Ru.
 3. The catalyst compound of claim 1, wherein Xand X¹ are independently selected from the group consisting of halides,alkoxides, aryloxides, and alkyl sulfonates.
 4. The catalyst compound ofclaim 1, wherein at least one of X and X¹ is a chloride.
 5. The catalystcompound of claim 1, wherein L¹ is O.
 6. The catalyst compound of claim1, wherein L is selected from the group consisting of a phosphine, anN-heterocyclic carbene, and a cyclic alkyl amino carbene.
 7. Thecatalyst compound of claim 1, wherein G* is selected from the groupconsisting of hydrogen, an alkyl, and a substituted alkyl.
 8. Thecatalyst compound of claim 1, wherein each G is independently, a C₁ toC₃₀ substituted or unsubstituted alkyl, or a substituted orunsubstituted C₄ to C₃₀ aryl.
 9. The catalyst compound of claim 1,wherein R¹ is a methoxy substituted phenyl.
 10. The catalyst compound ofclaim 1, wherein L and X are joined to form a multidentate monoanionicgroup or a dianionic group and form a single ring of up to 30non-hydrogen atoms or a multinuclear ring system of up to 30non-hydrogen atoms.
 11. A process to produce alpha-olefin comprisingcontacting an unsaturated fatty acid with an alkene and the catalystcompound of claim
 1. 12. A process to produce alpha-olefin comprisingcontacting a triacylglyceride with the catalyst compound of claim
 1. 13.A process to produce alpha-olefin comprising contacting an unsaturatedfatty acid ester and/or unsaturated fatty acid alkyl ester with analkene and the catalyst compound of claim
 1. 14. The process claim 13,wherein the alpha olefin is a linear alpha-olefin having 4 to 24 carbonatoms.
 15. The process of claim 13, wherein the alkene is ethylene,propylene, butene, hexene or octene.
 16. The process of claim 13, wherethe fatty acid alkyl ester is a fatty acid methyl ester.
 17. The processof claim 13, wherein the alpha-olefin is butene-1, decene-1 and/orheptene-1.
 18. A process to produce alpha-olefin comprising contacting afeed material with a metathesis catalyst compound represented by theformula:

wherein M is a Group 8 metal from the Periodic Table of the Elements; Xand X¹ are anionic ligands; L is a neutral two electron donor; L¹ is Oor S; R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substitutedhydrocarbyl; G* is selected from the group consisting of hydrogen, a C₁to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ isselected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl,and a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selectedfrom the group consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbylsand C₁ to C₃₀ substituted hydrocarbyls.
 19. The process of claim 18,wherein the feed material is a seed oil is selected from the groupconsisting of canola oil, corn oil, soybean oil, rapeseed oil, algaeoil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil,grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil,Jathropa oil, high-oleic soybean oil, high-oleic safflower oil,high-oleic sunflower oil, mixtures of animal and vegetable fats andoils, castor bean oil, dehydrated castor bean oil, cucumber oil,poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseedoil, meadowfoam, tuna oil, sesame oils and mixtures thereof.
 20. Theprocess of claim 18, wherein the feed material is selected from thegroup consisting of palm oil and algae oil.
 21. The process of claim 18wherein L¹ is O.
 22. A process to produce alpha-olefin comprisingcontacting a triacylglyceride with an alkene and a metathesis catalystcompound represented by the formula:

wherein M is a Group 8 metal from the Periodic Table of the Elements; Xand X¹ are anionic ligands; L is a neutral two electron donor; L¹ is Oor S; R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substitutedhydrocarbyl; G* is selected from the group consisting of hydrogen, a C₁to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ isselected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl,and a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selectedfrom the group consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbylsand C₁ to C₃₀ substituted hydrocarbyls; and wherein the alpha olefinproduced has at least one more carbon atom than the alkene.
 23. Theprocess of claim 22, wherein the triacylglyceride is contacted withalcohol and converted to a fatty acid ester or fatty acid alkyl esterprior to contacting with the catalyst compound.
 24. The process of claim22, wherein the triacylglyceride is contacted with water and convertedto a fatty acid prior to contacting with the catalyst compound.
 25. Theprocess of claim 22, wherein the productivity of the process is at least200 g of linear alpha-olefin per mmol of catalyst per hour.
 26. Theprocess of claim 22, wherein the selectivity of the process is at least20 wt% linear alpha-olefin, based upon the weight to the materialexiting the reactor.
 27. The process of claim 22, wherein the turnovernumber, defined as the moles of alpha olefin formed per mol of catalyst,of the process is at least 10,000.
 28. The process of claim 22, whereinthe yield, when converting unsaturated fatty acids, unsaturated fattyacid esters, unsaturated fatty acid alkyl esters or mixtures thereof, is30% or more, said yield being defined as the moles of alpha olefinformed per mol of unsaturated fatty acids, unsaturated fatty acidesters, unsaturated fatty acid alkyl esters or mixtures thereofintroduced into the reactor.
 29. The process of claim 28, wherein theyield is 60% or more.
 30. The process of claim 22, wherein the yield,when converting triacylglycerides as represented in the formula below,is 30% or more, said yield being defined as the moles of alpha olefinformed divided by (the total moles of unsaturated R^(a) , moles ofunsaturated R^(b) , and moles of unsaturated R^(c)) introduced into thereactor,

where R^(a), R^(b) and R^(c) each, independently, represent a saturatedor unsaturated hydrocarbon chain.
 31. The process of claim 22 wherein L¹is O.
 32. A process to produce alpha-olefin comprising contacting a feedmaterial with an alkene and a metathesis catalyst compound representedby the formula:

wherein M is a Group 8 metal from the Periodic Table of the Elements; Xand X¹ are anionic ligands; L is a neutral two electron donor; L¹ is Oor S; R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substitutedhydrocarbyl; G* is selected from the group consisting of hydrogen, a C₁to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ isselected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl,and a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selectedfrom the group consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbylsand C₁ to C₃₀ substituted hydrocarbyls and wherein the alpha olefinproduced has at least one more carbon atom than the alkene, wherein thefeed material is a triacylglyceride, fatty acid, fatty acid alkyl ester,and/or fatty acid ester derived from biodiesel.
 33. The process of claim32 wherein L¹ is O.
 34. A process to produce C₄ to C₂₄ linearalpha-olefin comprising contacting a feed material with an alkeneselected from the group consisting of ethylene, propylene butene,pentene, hexene, heptene, octene, nonene and mixtures thereof and ametathesis catalyst compound represented by the formula:

wherein M is a Group 8 metal from the Periodic Table of the Elements; Xand X¹ are anionic ligands; L is a neutral two electron donor; L¹ is Oor S; R is a C₁ to C₃₀ hydrocarbyl or a C₁ to C₃₀ substitutedhydrocarbyl; G* is selected from the group consisting of hydrogen, a C₁to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl; R¹ isselected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl,and a C₁ to C₃₀ substituted hydrocarbyl; and G is independently selectedfrom the group consisting of hydrogen, halogen, C₁ to C₃₀ hydrocarbylsand C₁ to C₃₀ substituted hydrocarbyls and wherein the alpha olefinproduced has at least one more carbon atom than the alkene, wherein thefeed material is a triacylglyceride, fatty acid, fatty acid alkyl ester,and/or fatty acid ester derived from seed oil.
 35. The process of claim34, wherein the alkene is ethylene, the alpha olefin is 1-butene,1-heptene and/or 1-decene, and the feed material is a fatty acid methylester, and/or fatty acid ester.
 36. The process of claim 34 wherein L¹is O.